| Titre : | Osmium(VIII) catalyzed oxidative cleavage of pyrrolidine ring in l-proline by hexacyanoferrate(III) in alkaline media (2010) |
| Auteurs : | K. Sharanabasamma, Auteur ; Mahantesh A. Angadi, Auteur ; Manjalee S. Salunke, Auteur |
| Type de document : | Article : texte imprimé |
| Dans : | Industrial & engineering chemistry research (Vol. 48 N° 23, Décembre 2009) |
| Article en page(s) : | pp. 10381–10386 |
| Note générale : | Industrial chemistry |
| Langues : | Anglais |
| Tags : | Osmium(VIII)--Catalyzed--Oxidative Cleavage--Pyrrolidine--Proline--Hexacyanoferrate(III)--Alkaline Media |
| Résumé : |
Kinetics of oxidation of l-proline by hexacyanoferrate(III) catalyzed by osmium(VIII) in alkaline medium was studied at 30 °C. A mechanism involving free radical path was proposed. Rate law of the reaction was derived as
The rate constant k and equilibrium constants K1 and K2 were evaluated as 3.79 × 103 dm3 mol−1 s−1, 0.52 dm3 mol−1, and 3.78 × 103 dm3 mol−1, respectively. The main reactive species of the catalyst appears to be OsO5(OH)3−. The oxidative product of l-proline was identified as l-glutamic acid which is different from the earlier reports. The literature reveals that 4-amino butyric acid, 4-amino butaraldehyde and keto acids were the oxidative products. Activation parameters were evaluated as Ea = 33.5 ± 2 kJ mol−1, ΔH⧧ = 31.0 ± 0.2 kJ mol−1, ΔS⧧ = −24 ± 1.5 J K−1 mol−1, ΔG⧧ = 38.0 ± 2 kJ mol−1. |
| ISSN : | 0888-5885 |
| En ligne : | http://pubs.acs.org/doi/abs/10.1021/ie901049p |
