Faculté des sciences

Oxidation of alkanes with m-chloroperbenzoic acid catalyzed by iron(III) chloride and a polydentate amine

Shul’pin, Georgiy B. ; Stoeckli-Evans, Helen ; Mandelli, Dalmo ; Kozlov, Yuriy N. ; Tesouro Vallina, Ana ; Woitiski, Camile B. ; Jimenez, Ricardo S. ; Carvalho, Wagner A.

In: Journal of Molecular Catalysis A: Chemical, 2004, vol. 219, no. 25, p. 255-264

Tetradentate amine N,N′-bis(2-pyridylmethylene)-1,4-diaminodiphenyl ether (compound 1) dramatically accelerates the oxidation of alkanes with MCPBA in acetonitrile catalyzed by FeCl3, whereas N,N′-bis(2-pyrrolidinmethylene)-1,4-diaminodiphenyl ether (2) does not affect the reaction. The selectivity of the reaction in the presence of 1 is... Plus

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    Summary
    Tetradentate amine N,N′-bis(2-pyridylmethylene)-1,4-diaminodiphenyl ether (compound 1) dramatically accelerates the oxidation of alkanes with MCPBA in acetonitrile catalyzed by FeCl3, whereas N,N′-bis(2-pyrrolidinmethylene)-1,4-diaminodiphenyl ether (2) does not affect the reaction. The selectivity of the reaction in the presence of 1 is noticeably higher than that in its absence. On the basis of the kinetic study and selectivity parameters a mechanism has been proposed which includes the formation of a complex between a molecule of MCPBA and coordinated to ligand 1 iron ion. This complex decomposes to produce a Fe(II) derivative which is further oxidized by MCPBA to generate a (1•Fe=O)4+ species reacting with both alkane and acetonitrile. Finally, alkyl hydroperoxide is formed which partially decomposes to produce more stable corresponding alcohol and ketone (aldehyde).