Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons Catalyzed by Montmorillonite or Aluminum Oxide
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Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons Catalyzed by Montmorillonite or Aluminum Oxide Dalmo Mandelli Æ Anielle C. N. do Amaral Æ Yuriy N. Kozlov Æ Lidia S. Shul’pina Æ Anderson J. Bonon Æ Wagner A. Carvalho Æ Georgiy B. Shul’pin
Received: 9 June 2009 / Accepted: 13 July 2009 / Published online: 24 July 2009 Springer Science+Business Media, LLC 2009
Abstract Montmorillonites K-10, Na0.60K0.12Ca0.02(Al1.78 Fe0.12Mg0.10)oct(Si3.89Al0.11)tetO10(OH)2, and NT-25, Na0.10 K0.04Ca0.08(Al1.28Fe0.45Mg0.28)oct(Si3.94Al0.06)tetO10(OH)2, and aluminum oxide, Al2O3, catalyze alkane hydroperoxidation and olefin epoxidation with hydrogen peroxide. Alkanes afford alkyl hydroperoxides as main primary products which partially decompose to produce corresponding ketones and alcohols. The oxidation of cis- and trans-isomers of 1,2-dimethylcyclohexane on K-10 proceeds stereoselectively. Benzene in the presence of montmorillonite K-10 is transformed into phenol. Styrene is oxidized to afford benzaldehyde and styrene epoxide. It is proposed on the basis of a kinetic study and measurements of the selectivity parameters that in the case of alumina the oxidation occurs with the participation of Electronic supplementary material The online version of this article (doi:10.1007/s10562-009-0103-z) contains supplementary material, which is available to authorized users. D. Mandelli A. C. N. do Amaral A. J. Bonon Faculdade de Quı´mica, Pontifı´cia Universidade Cato´lica de Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, Campinas, SP 13086-900, Brazil Y. N. Kozlov G. B. Shul’pin (&) Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, 119991 Moscow, Russia e-mail: [email protected]; [email protected] L. S. Shul’pina Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova, dom 28, 119991 Moscow, Russia W. A. Carvalho Centro de Cieˆncias Naturais e Humanas, Universidade Federal do ABC, Rua Catequese, 242, Bairro Jardim, Santo Andre´, SP 09090-400, Brazil
hydroxyl radicals generated from an aluminum peroxo derivative on the catalyst surface. In the cases of montmorillonites iron centers are also responsible for the H2O2 activation which gives hydroxyl radicals. Addition of trifluoroacetic acid (TFA) leads to the noticeable acceleration of all oxidation reactions and enhancement of the product yield. It has been shown that in the presence of TFA some parts of solid catalysts are transferred into the homogeneous solution. Thus, very cheap natural solid materials provide soluble species that are active in efficient homogeneous oxidations of hydrocarbons with hydrogen peroxide. In the absence of TFA the oxidation reactions in the case of the three catalysts are truly heterogeneous in nature. Keywords Alkanes Alkyl hydroperoxides Aluminum oxide Benzene Heterogeneous catalysis Hydrogen peroxide Montmorillonite Phenol
1 Introduction Hydroxylation and hydroperoxidation of saturated hydrocarbons is one of important
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