Publication Type |
Journal Article |
Title |
Hydrocarbon oxygenation with Oxone catalyzed by complex [Mn2L2O3](2+) (L=1,4,7-trimethyl-1,4,7-triazacyclononane) and oxalic acid |
Authors |
Georgiy B. Shul'pin Yuriy N. Koziov Lidia S. Shul?pina Armando J.L. Pombeiro |
Groups |
CCC |
Journal |
TETRAHEDRON |
Year |
2012 |
Month |
October |
Volume |
68 |
Number |
41 |
Pages |
8589-8599 |
Abstract |
Oxone (peroxysulphate) very efficiently oxidizes benzene to p-quinone (TON 1140) and alkanes to the corresponding alcohols and ketones (aldehydes) in aqueous acetonitrile 50 degrees C if catalytic amounts of complex [Mn2L2O3](2+) (L=1,4,7-trimethyl-1,4,7-triazacyclononane) and oxalic acid are present in the solution. In contrast to the similar reaction with H2O2, the alkane oxidation with Oxone does not afford the corresponding alkyl hydroperoxides. Phenol was quantitatively oxidized to a mixture of p-quinone and pyrocatechol (9:1 ratio). Cyclohexanol gave cyclohexanone (TON 400). The proposed mechanism includes the formation of an oxidizing species containing the Mn(V)=O fragment. A kinetic study demonstrated that an adduct of [Mn2L2O3](2+) and oxalic acid is formed in the initial stage. This adduct reacts with Oxone to generate the oxidizing species. (C) 2012 Elsevier Ltd. All rights reserved. |
DOI |
http://dx.doi.org/10.1016/j.tet.2012.07.098 |
ISBN |
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Publisher |
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Book Title |
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ISSN |
0040-4020 |
EISSN |
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Conference Name |
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Bibtex ID |
ISI:000308846100010 |
Observations |
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