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.
Oxidation of amines in the presence of ruthenium complexes : molecular oxygen and iodosylbenzene as oxidants / F. Porta, C. Crotti, S. Cenini, G. Palmisano. - In: JOURNAL OF MOLECULAR CATALYSIS. - ISSN 0304-5102. - 50:3(1989), pp. 333-341.
Oxidation of amines in the presence of ruthenium complexes : molecular oxygen and iodosylbenzene as oxidants
F. Porta;
1989
Abstract
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.
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