Abstract
Data on the kinetics, kinetic isotope effects, substrate selectivety, and activation parameters for the first step of oxidation of alkylbenzenes by permanganante in acidic aqueous solutions are surveyed. The MnO4 −, HMnO4, and MnO3 + species serve as oxidants at different acidities. The increase in the positive charge in this series enhances the electrophilicity of the reagent, which manifests itself as an increase in the reaction rate and a change in the site of attack on the alkylbenzene molecule (either the aromatic ring or C−H bond in the alkyl group). The oxidation of the alkyl C−H bonds in alkylbenzenes and in alkanes follows similar mechanisms, while the attack on the aromatic ring proceedsvia the electrophilic aromatic substitution mechanism with a transition state intermediate between the charge transfer complex and σ-complex.
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References
Y. Ogata,Kagaku no Ryoiki, 1973,27, 941.
U. A. Spitzer and R. Stewart,Can. J. Chem., 1978,56, 1273.
E. S. Rudakov and L. K. Volkova,Kinet Katal., 1983,24, 542 [Kinet. Catal., 1983,24 (Engl. Transl.)].
E. S. Rudakov and V. L. Lobachev,Kinet Katal., 1994,35, 198 [Kiner. Catal., 1994,35 (Engl. Transl.)].
V. L. Lobachev and E. S. Rudakov,Kinet Katal., 1994,35, 203 [Kinet. Catal., 1994,35 (Engl. Transl.)].
E. S. Rudakov,Reaktsii alkanov s okislitelyami, metallokompleksami i radikatami v rastvorakh [Reactions of Alkanes with Oxidants, Metal Complexes, and Radicals in Solutions], Naukova Dumka, Kiev, 1985, 244 pp. (in Russian).
D. L. Lee and B. E. Singer,Can. J. Chem., 1970,48, 2674.
K. B. Wiberg and A. S. Fox,J. Am. Chem. Soc., 1963,85, 3487.
D. G. Lee and T. Chen,J. Am. Chem. Soc., 1993,115, 11231.
P. K. Sen, A. Sanyal, and K. K. Sengupta,J. Ind. Chem. Soc., 1993,70, 341.
P. K. Sen, A. Sanyal, and K. K. Sengupta,Int. J. Chem. Kinet., 1995,27, 379.
A. Thibblin,J. Phys. Organ. Chem., 1995,8, 186.
M. Starks,J. Am. Chem. Soc., 1971,93, 195.
N. A. Gibson and J. W. Hosking,Austr. J. Chem., 1965,18, 123.
K. Nakemura, S. Nishiyama, S. Tsuruya, and M. Massai,J. Mol. Catal., 1994,93, 195.
S. Dash and B. K. Mishra,Int. J. Chem. Kinet., 1995,27, 627.
V. Holba and R. Sumicharast,Monats. Chem., 1995,126, 681.
E. S. Rudakov,Kinet Katal., 1960,1, 528 [Kinet. Catal., 1960,1 (Engl. Transl.)].
E. S. Rudakov, I. V. Kozhevnikov, and V. V. Zamashchikov,Usp. Khim., 1975,43, 707 [Russ. Chem. Rev., 1975,43 (Engl. Transl.)].
E. S. Rudakov, A. P. Yaroshenko, and V. V. Zamashchikov,React. Kinet. Catal. Lett., 1981,17, 7.
V. L. Lobachev, E. S. Rudakov, and A. I. LutsykDokl. Akad. Nauk UkrSSR, Ser. B [Bull. Ukrainian Acad. Sci., Ser. B], 1980, 51 (in Russian).
E. S. Rudakov and V. L. Lobachev,Kinet. Katal., 1988,29, 1056 [Kinet. Catal., 1988,29 (Engl. Transl.)].
V. M. Ignatenko and E. S. Rudakov,Kinet. Katal., 1989,30, 44 [Kinet. Catal., 1989,30 (Engl. Transl.)].
E. S. Rudakov, V. L. Lobachev, V. M. Ignatenko, and L. I. Velichko,Kinet. Katal., 1986,27, 1315 [Kinet. Catal., 1986,27 (Engl. Transl.)].
V. L. Lobachev, E. S. Rudakov, and O. B. Savsunenko,Kinet Katal., 1990,31, 789 [Kinet. Cata., 1990,31 (Engl. Transl.)].
E. S. Rudakov, V. L. Lobachev, and S. A. Tserkovnikov,Kinet Katal., 1993,34, 439 [Kinet. Catal., 1993,34 (Engl. Transl.)].
J. B. Levy, R. W. Taft, D. Aaron, and L. P. Hammet,J. Am. Chem. Soc., 1951,73, 3792.
K. H. Heckner, S. Dalchan, and R. Landsberg,J. Prakt. Chem., 1971,313, 155.
K. B. Wiberg and R. Stewart,J. Am. Chem. Soc., 1955,77, 1786.
M. Jaky and S. Szabo,Ach-Models in Chem., 1995,132, 739.
D. G. Lee and T. Chen,J. Am. Chem. Soc., 1989,111, 7534.
T. Ogino and N. Kikuiri,J. Am. Chem. Soc., 1989,111, 6174.
D. J. Nelson and R. L. Henley,Tetrahedron Lett., 1995,36, 6375.
E. S. Rudakov and V. L. Lobachev,Izv. Sib. Otd Akad. Nauk SSSR, Ser. Khim. Nauk [Bull. Sib. Branch USSR Acad. Sci., Div. Chem. Sci.], 1987, 25 (in Russian).
J. Hanotier, R. Camerman, M. Hanotier-Bridoux, and P. de Radzitzky,J. Chem. Soc., Perkin Trans. 2, 1972, 2247.
A. K. Yatsimirskii and I. V. Berezin,Kinet Katal., 1976,17, 1191 [Kinet. Catal., 1976,17 (Engl. Transl.)].
I. V. Kozhevnikov, V. I. Kim, E. P. Talzi, and V. N. Sidelnikov,J. Chem. Soc., Chem. Commun., 1985, 1392.
E. S. Rudakov, N. A. Tishchenko, and L. K. Volkova,Kinet. Katal., 1986,27, 1101 [Kinet. Catal., 1986,27 (Engl. Transl.)].
E. S. Rudakov, and N. A. Tishchenko,Dokl. Akad. Nauk SSSR, 1985,253, 181 [Dokl. Chem., 1985 (Engl. Transl.)].
E. S. Rudakov,Kinet Katal., 1964,5, 178 [Kinet. Catal., 1964,5 (Engl. Transl.)].
E. S. Rudakov,Kinet Katal., 1960,1, 177 [Kinet. Catal., 1960,1 (Engl. Transl.)].
E. S. Rudakov, V. L. Lobachev, Yu. V. Geletti, and Zh. Zh. A. Balavuen,Zh. Org. Khim., 1996,32, 522 [Russ. J. Org. Chem., 1996,32 (Engl. Transl.)].
V. P. Tret'yakov, G. P. Zimtseva, and E. S. Rudakov,Kinet Katal., 1998,39, 227 [Kinet. Catal., 1998,39 (Engl. Transl.)].
E. S. Rudakov and R. I. Rudakova,Dokl. Akad. Nauk SSSR, 1974,218, 1377 [Dokl. Chem., 1974 (Engl. Transl.)].
E. S. Rudakov, V. V. Zamashchikov, A. I. Lutsyk, and G. P. Zimtseva,Zh. Fiz. Khim., 1975,49, 2729 [J. Phys. Chem. USSR, 1975,49 (Engl. Transl.)].
E. S. Rudakov, V. V. Zamashchikov, A. I. Lutsyk, and I. R. Chanysheva,Dokl. Akad. Nauk UkrSSR, Ser. B [Bull. Ukrainian Acad. Sci., Ser. B], 1976, 338 (in Russian).
E. S. Rudakov, V. V. Zamashchikov, and A. I. Lutsyk,Dokl. Akad. Nauk UkrSSR, Ser. B [Bull. Ukrainian Acad. Sci., Ser. B], 1975, 813 (in Russian).
E. S. Rudakov, L. K. Volkova, and V. P. Tretyakov,React. Kinet. Catal. Lett., 1982,21, 357.
E. S. Rudakov, A. I. Lutsyk, and S. Yu. Suikov,Ukr. Khim. Zh., 1983,49, 970 [Ukr. J. Chem., 1983,49 (Engl. Transl.)].
E. S. Rudakov and N. A. Tishchenko,Kinet. Katal., 1990,31, 1079 [Kinet. Catal., 1990,31 (Engl. Transl.)].
E. S. Rudakov and N. A. Tishchenko,Kinet. Katal., 1991,32, 274 [Kinet. Catal., 1991,32 (Engl. Transl.)].
E. S. Rudakov and R. I. Rudakova,Dokl. Akad. Nauk UkrSSR, Ser. B [Bull. Ukr. Acad. Sci., Ser. B], 1979,46 (in Russian).
E. S. Rudakov,Dokl. Akad. Nauk UkrSSR, Ser. B [Bull. Ukr. Acad. Sci., Ser. B], 1984, 666 (in Russian).
J. K. Kochi, R. T. Tang, and T. Bernath,J. Am. Chem. Soc., 1973,95, 7114.
K. Nyberg and L. G. Wistrand,Chem. Scr., 1974,6, 234.
W. Lau and J. K. Kochi,J. Am. Chem. Soc., 1984,106, 7100.
I. P. Beletskaya and D. I. Makhon'kov,Usp. Khim., 1981,50, 1007 [Russ. Chem. Rev., 1981,50 (Engl. Transl.)].
J. Hanotier, M. Hanotier-Bridoux, and P. de Radzitzky,J. Chem. Soc., Perkin Trans. 2, 1973, 381.
W. Lau and J. K. Kochi,J. Am. Chem. Soc., 1986,108, 6720.
V. P. Tret'yakov, G. P. Zimtseva, L. K. Min'ko, and E. S. Rudakov,Ukr. Khim. Zh., 1990,56, 51 [Ukr. J. Chem., 1990,56 (Engl. Transl.)].
P. M. Henry,Palladium-Catalyzed Oxidation of Hydrocarbons, Reidel, Dordrecht, 1980,2, 435 pp.
I. V. Kozhevnikov,Usp. Khim., 1983,52, 244 [Russ. Chem. Rev., 1983,52 (Engl. Transl.)].
C. K. Ingold,Structure and Mechanism of Organic Chemistry, 2nd ed., Cornell University Press, Ithaca-London, 1969.
G. A. Olah, S. Kobayashi, and M. Tashiro,J. Am. Chem. Soc., 1972,94, 7448.
S. Nagakura,Tetrahedron, 1963,19, 361.
E. R. Pedersen, T. E. Petersen, K. Torsell, and S. O. Lawesson,Tetrahedron, 1973,29, 579.
V. A. Koptyug,Arenonievye iony: stroenie i reaktsionnaya sposobnost” [Arenonium Ions: Structure and Reactivity], Nauka, Novosibirsk, 1983, 270 pp. (in Russian).
C. L. Perrin,J. Am. Chem. Soc., 1977,99, 5516.
A. Streitwieser, Jr.,Molecular Orbital Theory for Organic Chemists, J. Wiley and Sons, New York-London, 1961.
G. A. Olah and S. J. Kuhn,J. Am. Chem. Soc., 1958,80, 6541.
T. M. bockman and J. K. Kochi,J. Phys. Org. Chem., 1994,7, 325.
L. M. Stock and H. C. Brown,Adv. Phys. Org. Chem., 1963,1, 35.
C. Gali and S. di Giammarino,J. Chem. Soc., Perkin Trans. 2, 1994, 1261.
V. A. Koptyug, O. Yu. Rogozhnikova, and A. N. Detsina,Zh. Org. Khim., 1983,19, 363 [J. Org. Chem. USSR, 1983,19 (Engl. Transl.)].
E. S. Rudakov and V. L. Lobachev,Kinet. Katal., 1990,31, 1302 [Kinet. Catal., 1990,31 (Engl. Transl.)].
K. Watanabe, T. Nakajama, and J. Mottl,Quant. Spectrosc. Radiat. Transfer, 1962,2, 369.
E. S. Rudakov, V. L. Lobachev, and O. B. Savsunenko,Kinet. Katal., 1990,31, 795 [Kinet. Catal., 1990,31 (Engl. Transl.)].
V. L. Lobachev,Teor. Eksp. Khim., 1999,35, 39 [Theor. Exp. Chem., 1999,35 (Engl. Transl.)].
D. J. Royer,J. Inorg. Nucl. Chem., 1961,17, 159.
H. C. Mishra and M. C. R. Symons,J. Chem. Soc., 1962, 4411.
N. Bailey, A. Carrington, K. A. K. Lott, and M. C. R. Symons,J. Chem. Soc., 1960, 290.
V. Ya. Shafirovich, N. K. Khannanov, and A. E. Shilov,Kinet. Katal., 1978,19, 1498 [Kinet. Catal., 1978,19 (Engl. Transl.)].
V. L. Lobachev, E. S. Rudakov, and E. V. Zaichuk,Kinet. Katal., 1997,38, 825 [Kinet. Catal., 1997,38 (Engl. Transl.)].
R. Stewart and M. M. Mocek,Can. J. Chem., 1963,41, 1160.
F. A. Cotton and G. Wilkinson,Advanced Inorganic Chemistry. A Comprehensive Text, 2nd ed., J. Wiley and Sons, New York-London-Sydney, 1967.
V. Ya. Shafirovich, N. K. Khannanov, and A. E. Shilov,Kinet. Katal., 1978,19, 1502 [Kinet. Catal., 1978,19 (Engl. Transl.)].
V. Ya. Shafirovich and A. E. Shilov,Kinet. Katal., 1979,20, 1156 [Kinet. Catal., 1979,20 (Engl. Transl.)].
A. V. Iogansen, N. A. Kovalenko, and O. V. Levina,Khim. Fiz., 1982,4, 524 [Sov. Chem. Phys., 1982,4 (Engl. Transl.)].
M. J. Insausti, F. Mataperes, and M. P. Alvarezmacho,Coll. Czech. Chem. Commun., 1996,61, 232.
M. J. Insausti, F. Mataperes, and M. P. Alvarezmacho,Int. J. Chem. Kinet., 1995,27, 507.
R. H. Boyd,J. Am. Chem. Soc., 1961,83, 4288.
Voprosy fizicheskoi khimii rastvorov elektrolitov [Problems of the Physical Chemistry of Electrolyte Solutions], Ed. G. I. Mikulin, Khimiya, Leningrad, 1968, 418 pp. (in Russian).
U. A. Spitzer, T. W. Toone, and R. Stewart,Can. J. Chem., 1976,54, 440.
E. S. Lewis and J. K. Robinson,J. Am. Chem. Soc., 1968,90, 4337.
J. I. Brauman and A. J. Pandell,J. Am. Chem. Soc., 1970,92, 329.
E. S. Rudakov, V. L. Lobachev, and E. V. Zaichuk,Kinet. Katal., 1996,37, 180 [Kinet. Catal., 1996,37 (Engl. Transl.)].
Energii razryvaa khimicheskikh svyazei. Potentsialy ionizatsii i srodstvo k elektronu [Energies of the Cleavage of Chemical Bonds. Ionization Potentials and Electron Affinity], Ed. V. N. Kondrat'ev, Nauka, Moscow, 1974, 351 pp. (in Russian).
E. S. Rudakov, V. L. Lobachev, and E. V. Zaichuk,Kinet. Katal., 1996,37, 534 [Kinet. Catal., 1996,37 (Engl. Transl.)].
E. T. Denisov,Konstanty skorosti gomoliticheskikh zhidkofaznykh reaktsii [Rate Constants of Homolytic Liquid-Phase Reactions], Nauka, Moscow, 1971, 711 pp. (in Russian).
R. C. Dobson, D. M. Hayes, and R. Hoffman,J. Am. Chem. Soc., 1971,93, 6188.
N. Bodor, M. J. S. Dewar, and J. S. Wasson,J. Am. Chem. Soc., 1972,94, 9095.
E. I. Karasevich, A. F. Shestakov, and A. E. Shilov,Kinet. Katal., 1997,38, 852 [Kinet. Catal., 1997,38 (Engl. Transl.)].
K. A. Gardner,Science, 1995,269, 1849.
W. Rüttinger and G. C. Dismukes,Chem. Rev., 1997,97, 1.
K. A. Gardner, L. L. Kuehnert, and J. M. Mayer,Inorg. Chem., 1997,36, 2069.
T. C. Lau, Z. B. Wu, Z. L. Bai, and C. K. Mak,J. Chem. Soc., Dalton Trans., 1995, 695.
E. Nomura, H. Taniguchi, and Y. Otsuji,Bull. Chem. Soc. Jpn., 1994,67, 309.
L. K. Lin and C. S. Lin,J. Clin. Chem. Soc., 1996,43, 61.
V. L. Lobachev and E. S. Rudakov,Kinet. Katal., 1995,36, 538 [Kinet. Catal., 1995,36 (Engl. Transl.)].
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 765–780, May, 2000.
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Rudakov, E.S., Lobachev, V.L. The first step of oxidation of alkylbenzenes by permanganates in acidic aqueous solutions. Russ Chem Bull 49, 761–777 (2000). https://doi.org/10.1007/BF02494695
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DOI: https://doi.org/10.1007/BF02494695