The intermediate formed during the oxidation of benzylamine with molecular oxygen at atmospheric pressure and 80 °C to yield the corresponding nitrile catalyzed by Ru(PPh3)2(RCH2NH2)2 Cl2 (I) (a reaction previously studied), has been shown to be Ru(PPh3)(RCN)(RCH2NH2)Cl2 (R = C6H5, p-CH3OC6H4) (II). A complex such as cis-Ru(bipy)2Cl2· 2H2O (bipy = 2,2'-bipyridine) is inactive as catalyst in this reaction, the only product isolated being [Ru(bipy)2(RCH2NH2)Cl] C1·2H2O (R = C6H5) (III). Dibenzylamine, (PhCH2)2NH, is oxidized to N-benzylidenebenzylamine, PhCHNCH2Ph, by molecular oxygen at atmospheric pressure and 80 °C in the presence of Ru(PPh3)3Cl2 and Ru(DMSO)4Cl2 as catalysts. Other secondary amines were not oxidized or gave intractable products, as in the case of N-benzylmethylamine. lodosylbenzene, PhIO, has been shown to be a very active and selective oxidant of primary and secondary amines at room temperature, its activity being negatively modified by the presence of Ru(PPh3)3Cl2.
|Titolo:||Oxidation of amines in the presence of ruthenium complexes : molecular oxygen and iodosylbenzene as oxidants|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||1989|
|Digital Object Identifier (DOI):||10.1016/0304-5102(89)80289-5|
|Appare nelle tipologie:||01 - Articolo su periodico|