III International Conference

PP-I-33HYDROGEN PEROXIDE OXIDATION OF SATURATED HYDROCARBONSCATALYZED BY IRON(III) CHLORIDE AND 2,2’-BIPYRIDINEMandelli D., Shul’pina L.S. 1 , Golfeto C.C., Shul’pin G.B. 2Pontifícia Universidade Católica de Campinas, Faculdade de Química, Rod. D. Pedro I,km 136, Pq. das Universidades, Campinas, SP, 13086-900, Brazil1Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,Moscow, Russia2N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, RussiaE-mail: dalmo_mandelli@mail.ruThe H 2 O 2 –FeCl 3 –bipy system in acetonitrile efficiently oxidizes alkanes predominantlyto alkyl hydroperoxides. Turnover numbers attain 500 after 1 h at 60 ºC. It has been assumedthat bipy facilitates proton abstraction from a H 2 O 2 molecule coordinated to the iron ion(these reactions are stages in the catalytic cycle generating hydroxyl radicals from thehydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkylhydroperoxide.In the course of our studies of iron-catalyzed hydrocarbon oxygenations with peroxides[1] we explored the possibility of enhancing the reaction efficiency by addition of certainamines. Here we report that 2,2’-bipyridine added to iron(III) chloride used as a catalystaccelerates oxidation of alkanes with hydrogen peroxide in acetonitrile. Main features of thereaction will be discussed.Acknowledgments. This work was supported by the Russian Basic Research Foundation(06-03-32344-a), the State of São Paulo Research Foundation (FAPESP, 2002/08495-4,06/03984-8), the Brazilian National Council on Scientific and Technological Development(CNPq, 300984/2004-9, 300601/01-8). G. B. Sh. expresses his gratitude to FAPESP, CNPq,Faculdade de Química, Pontifícia Universidade Católica de Campinas (PUC) for making itpossible for him to stay at PUC as invited Professor and to perform a part of the present work.References1. G. B. Shul’pin, J. Mol. Catal., A: Chem. 2002, 189, 39–66. G. B. Shul’pin, Comptes Rend. Chim.2003, 6, 163–178. G. V. Nizova; B. Krebs; G. Süss-Fink; S. Schindler; L. Westerheide;L. Gonzalez Cuervo; G. B. Shul’pin, Tetrahedron 2002, 58, 9231–9237. G. B. Shul’pin;H. Stoeckli-Evans; D. Mandelli; Y. N. Kozlov; A. Tesouro Vallina; C. B. Woitiski;R. S. Jimenez; W. A. Carvalho, J. Mol. Catal. A: Chem. 2004, 219, 255–264. G. B. Shul’pin;G. V. Nizova; Y. N. Kozlov; L. Gonzalez Cuervo; G. Süss-Fink, Adv. Synth. Catal. 2004, 346,317–332. G. B. Shul’pin, C. C. Golfeto, G. Süss-Fink, L. S. Shul’pina, D. Mandelli, TetrahedronLett., 2005, 46, 4563–4567.67