Abstract
The catalytic effects of small amounts of water (∼10−3 mol/l) added to the ethylbenzene oxidation reaction with molecular oxygen catalyzed by the system {Fe(III)(acac)3 + 18-crown-6 (18C6)} were revealed. An increase in the reaction rate was observed, and the direction of the oxidation reaction changed. In the presence of the catalytic system {Fe(III)(acac)3 (5.0 × 10−3 mol/l) + 18C6 (5.0 × 10−3 mol/l) + H2O (3.7 × 10−3 mol/l}, the main product at early stages of ethylbenzene oxidation is acetophenone, rather than α-phenylethyl hydroperoxide produced in the case of catalysis by the system {Fe(III)(acac)3 (5.0 × 10−3 mol/l) + 18C6 (5.0 × 10−3 mol/l)} (in the absence of water admixture). A method is proposed to evaluate the activity of forming in situ (Fe(II)(acac)2) x (18C6) y (H2O) n complexes at microstages of chain initiation (O2 activation) and propagation (Ct+RO ·2 ) involving the catalyst, which determine the rate and selectivity of oxidation. A possible “dioxygenase-like” mechanism of conversion of iron complexes with 18C6 in the presence of activating H2O admixtures is discussed.
Similar content being viewed by others
References
K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry (VCH, New York, 1997).
L. I. Matienko, in Chemical Reaction in Condensed Phase: The Quantitative Level, Ed. by G. E. Zaikov, V. G. Zaikov, and A. K. Mikitaev (Nova Science, New York, 2006), p. 49.
E. I. Karasevish, V. S. Kulikova, A. E. Shilov, and A. A. Shteinman, Usp. Khim. 67, 376 (1998).
D. Mansuy, in The Activation of Dioxygen and Homogeneous Catalytic Oxidation, Ed. by D. H. R. Barton, A. E. Martell, and D. T. Sawyer (Plenum, New York, 1993), p. 347.
L. A. Mosolova, L. I. Matienko, and I. P. Skibida, Kinet. Katal. 28, 479 (1987).
L. A. Mosolova, L. I. Matienko, and I. P. Skibida, Kinet. Katal. 28, 484 (1987).
L. I. Matienko, L. A. Mosolova, and I. P. Skibida, Izv. Akad. Nauk, Ser. Khim., No. 8, 1412 (1994).
L. I. Matienko and L. A. Mosolova, Kinet. Katal. 44, 237 (2003).
L. I. Matienko and L. A. Mosolova, Kinet. Katal. 46, 354 (2005).
L. I. Matienko and L. A. Mosolova, in Progress in Heterogeneous Catalysis and Heterocycles Ed. by D. L. Rakhmankulov (Khimiya, Moscow, 2006), p. 235.
L. I. Matienko and L. A. Mosolova, in New Aspects of Biochemical Physics. Pure and Applied Sciences, Ed. by S. D. Varfolomeev, E. B. Burlakova, A. A. Popov, and G. E. Zaikov (Nova Science, New York, 2006), p. 128.
L. I. Matienko and L. A. Mosolova, Neftekhimiya 47, 42 (2007) [Pet. Chem. 47, 39 (2007)].
G. D. Straganz and B. Nidetzky, J. Am. Chem. Soc. 127, 12306 (2005).
Y. Dai, Th. C. Pochapsky, and R. H. Abeles, Biochemistry 40, 6379 (2001).
B. Gopal, L. L. Madan, S. F. Betz, and A. A. Kossiakoff, Biochemistry 44, 193 (2005).
E. Balogh-Hergovich, J. Kaizer, and G. Speier, J. Mol. Catal., A: Chem. 159, 215 (2000).
J. H. Nelson, P. N. Howels, G. L. Landen, et al., in Fundamental Research in Homogeneous Catalysis (Plenum, New York, 1979), Vol. 49, p. 921.
L. Pardo, R. Osman, H. Weinstein, and J. R. Rabinowitz, J. Am. Chem. Soc. 115, 8263 (1993).
E. Dehmlow and S. Dehmlow, Phase Transfer Catalysis (Chemie, Weinheim, 1983; Mir, Moscow, 1987).
L. I. Matienko and L. Mosolova, Oxid. Commun. (in press).
A. M. Klibanov, Acc. Chem. Res. 23, 114 (1990).
Li Hua, L. Yangzhong, Z. Xuhong, et al., J. Am. Chem. Soc. 128, 6391 (2006).
N. M. Emanuel, G. E. Zaikov, and Z. K. Maizus, The Effect of Medium in Radical-Chain Oxidation of Organic Compounds (Nauka, Moscow, 1973) [in Russian].
W. Partenheimer, Catal. Today 23, 69 (1991).
V. A. Golodov, Ross. Khim. Zh. 44(3), 45 (2000).
V. K. Bel’skii and B. M. Bulychev, Usp. Khim. 68, 136 (1999).
E. M. Kuramshin, M. V. Kochinashvili, S. S. Zlotskii, and D. P. Rakhmankulov, Dokl. Akad. Nauk SSSR 279, 1392 (1984).
I. Goldberg, Acta Crystallogr. 34, 3387 (1978).
J. Jaguar-Grodzinnski, Isr. J. Chem. 25, 39 (1985).
V. M. Nekipelov and K. I. Zamaraev, Coord. Chem. Rev. 61, 185 (1985).
L. J. Csanyi, K. Jaky, and G. Galbacs, J. Mol. Catal., A: Chem. 164, 109 (2000).
L. J. Csanyi, K. Jaky, G. Dombi, et al., J. Mol. Catal., A: Chem. 195, 109 (2003).
L. J. Csanyi, K. Jaky, I. Palinko, et al., Phys. Chem. Chem. Phys., No. 2, 3801 (2000).
N. M. Emanuel, E. T. Denisov, and Z. K. Maizus, Liquid-Phase Oxidation of Hydrocarbons (Nauka, Moscow, 1965; Plenum, New York, 1967).
A. E. Semenchenko, V. M. Solyanikov, and E. T. Denisov, Zh. Fiz. Khim. 47, 1148 (1973).
F. A. Chavez, J. M. Rowland, M. M. Olmstead, and P. K. Mascharak, J. Am. Chem. Soc. 120, 9015 (1998).
E. Solomon-Rapaport, A. Masarwa, H. Cohen, and D. Meyerstein, Inorg. Chim. Acta 299, 41 (2000).
D. Krishnamurthy, G. D. Kasper, F. Namuswe, et al., J. Am. Chem. Soc. 128, 14222 (2006).
M. J. Carter, D. P. Rillema, and F. Basolo, J. Am. Chem. Soc. 96, 392 (1974).
A. L. Balch, R. L. Hart, L. Latos-Grazynski, and T. G. Traylor, J. Am. Chem. Soc. 112, 7382 (1990).
N. Komiya, T. Naota, and Sh.-I. Murahashi, Tetrahedron Lett. 37, 1633 (1996).
H. Rudler and B. Denise, J. Mol. Catal., A: Chem. 154, 277 (2000).
Ch. K. Kang, Ch. Redman, V. Cepak, and D. T. Sawyer, Bioorg. Med. Chem. 1, 125 (1991).
T. Matsushita, D. T. Sawyer, and A. Sobkowiak, J. Mol. Catal., A: Chem. 137, 127 (1999).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © L.I. Matienko, L.A. Mosolova, 2008, published in Neftekhimiya, 2008, Vol. 48, No. 5, pp. 368–377.
Rights and permissions
About this article
Cite this article
Matienko, L.I., Mosolova, L.A. Effect of small concentrations of water on ethylbenzene oxidation with molecular oxygen catalyzed by iron(II, III) acetylacetonate complexes with 18-crown-6. Pet. Chem. 48, 371–380 (2008). https://doi.org/10.1134/S0965544108050071
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0965544108050071