G. B. Shul’pin, Activation and Catalytic Reactions of Hydrocarbons,
Nauka, Moscow, 1995.
described in this paper is one of the most efficient ones (in terms
of catalytic turnovers) for methane oxidation8 under mild
conditions (temperatures below 100 °C).
We thank BASF, the International Science Foundation,
INTAS, the Russian Basic Research Foundation and the Swiss
National Science Foundation for support and Dr. Arthur Ho¨hn
(BASF, Ludwigshafen, Germany) for fruitful discussions.
2 A. Butler, M. J. Clague and G. E. Meister, Chem. Rev., 1994, 94, 625;
M. Bonchio, V. Conte, F. Di Furia, G. Modena, S. Moro, T. Carofiglio,
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Footnotes
3 G. B. Shul’pin, D. Attanasio and L. Suber, Russ. Chem. Bull., 1993, 42,
55; G. B. Shul’pin, D. Attanasio and L. Suber, J. Catal., 1993, 142, 147;
G. B. Shul’pin, A. N. Druzhinina and G. V. Nizova, Russ. Chem. Bull.,
1993, 42, 1326; G. V. Nizova and G. B. Shul’pin, Russ. Chem. Bull.,
1994, 43, 1146; G. B. Shul’pin and G. Su¨ss-Fink, J. Chem. Soc., Perkin
Trans. 2, 1995, 1459; G. B. Shul’pin, R. S. Drago and M. Gonzalez, Russ.
Chem. Bull., 1996, 45, 2386; M. C. Guerreiro, U. Schuchardt and
G. B. Shul’pin, Russ. Chem. Bull., in the press; G. B. Shul’pin,
M. C. Guerreiro and U. Schuchardt, Tetrahedron, 1996, 52, 13 051.
4 (a) G. B. Shul’pin and A. N. Druzhinina, Mendeleev Commun., 1992, 36;
(b) React. Kinet. Catal. Lett., 1992, 47, 207; (c) G. B. Shul’pin and
G. V. Nizova, React. Kinet. Catal. Lett., 1992, 48, 333; (d) G. B. Shul’pin,
A. N. Druzhinina and L. S. Shul’pina, Neftekhimiya, 1993, 33, 335; (e)
G. B. Shul’pin, M. M. Bochkova and G. V. Nizova, J. Chem. Soc., Perkin
Trans. 2, 1995, 1465.
† E-mail: Suess-Fink@ich.unine.ch
‡ E-mail: gb@shulpin.msk.ru
§ The oxidations were carried out in glass-lined stainless-steel autoclaves
with vigorous stirring (volume of the reaction solution = 10 ml, total
volume of autoclave = 100 ml). Usually the following concentrations of the
reagents were used: [NBu4]VO3, 1.0 3 1024 mol dm23; PCA, 4.0 3 1024
mol dm23; H2O2 (35% aq), 0.2 mol dm23. Before the oxidation the
autoclave was charged with air and then with methane under appropriate
pressures. (CAUTION: the combination of air and H2O2 with organic
compounds at elevated pressures and temperatures may be explosive!) The
reactions were stopped by cooling with ice and the reaction solution was
analysed by GC (DANI-86.10; fused silica capillary column 60 m 3 0.25
mm 3 0.25 mm, SPB-1; integrator SP-4400). The concentration of
formaldehyde was measured spectrophotometrically after its transformation
into 2,6-dimethyl-3,5-diacetyl-1,4-dihydropyridine according to method
described in ref. 9.
5 D. L. Vanoppen, D. E. De Vos, M. J. Genet, P. G. Rouxhet and
P. A. Jacobs, Angew. Chem., Int. Ed. Engl., 1995, 34, 560.
¶ If an excess of solid PPh3 is added to the reaction solution 10–20 min
before the GC analysis, the alkyl hydroperoxide present is completely
reduced to the corresponding alcohol. As a result, the chromatogram differs
completely from that of a sample not subjected to the reduction (the alcohol
peak increases, while the intensity of the ketone peak decreases). If there is
no difference between chromatograms of the same sample before and after
reduction, this testifies to the absence of an alkyl hydroperoxide in the
solution. If, by contrast, the chromatogram prior to the reduction exhibits
the peaks for the ketone and the alcohol, whereas after the reduction with
PPh3 only a peak for the alcohol is observed, one may conclude that only the
alkyl hydroperoxide was present in the solution. This method allows one to
determine alkyl hydroperoxides in the presence of hydrogen peroxide.
∑ The reaction was carried out in a sealed ampoule (10 ml) at 20 °C under
an atmospheric pressure of 18O2 (content 98%, Cambridge Isotope
6 I. W. C. E. Arends, K. U. Ingold and D. D. M. Wayner, J. Am. Chem. Soc.,
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7 U. Schuchardt, D. Mandelli and G. B. Shul’pin, Tetrahedron Lett., 1996,
37, 6487.
8 P. E. Ellis, Jr. and J. E. Lyons, Coord. Chem. Rev., 1990, 105, 181;
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G. Voss and T. Masuda, Science, 1993, 259, 340; M. W. Grinstaff,
M. G. Hill, J. A. Labinger and H. B. Gray, Science, 1994, 264, 1311;
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K. Takaki and Y. Fujiwara, Chem. Lett., 1995, 244; Y. Taniguchi,
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Laboratories) over 3 days; concentrations: cyclohexane, 0.46 mol dm23
;
H2O2 (35% aq), 0.2 mol dm23; [NBu4]VO3, 1.0 3 1024 mol dm23, PCA,
4.0 3 1024 mol dm23. The resulting solution was analysed by GCMS
(NERMAG R 30-10, capillary column 50 m 3 0.25 mm 3 0.25 mm,
Carbowax 20M).
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