HOMOGENEOUS CATALYTIC OXIDATION OF LIGHT ALKANES
×
102, mol/l
671
ACKNOWLEDGMENTS
Concentration
22
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 09ꢀ03ꢀ00387) and
the Council of the President of the Russian Federation
for Support for Young Scientists and Leading Scienꢀ
tific Schools (grant no. NSh 1733.2008.3).
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REFERENCES
1. Shilov, A.E. and Shul’pin, G.B., Aktivatsiya i kataliꢀ
ticheskie reaktsii uglevodorodov (Activation and Cataꢀ
lytic Reactions of Hydrocarbons), Moscow: Nauka,
1995.
2. Moiseev, I.I., Kinet. Katal., 2001, vol. 42, p. 5 [Kinet.
Catal. (Engl. Transl.), vol. 42, p. 1].
6
4
4
2
3. Sen, A., Acc. Chem. Res., 1998, vol. 31, p. 550.
4. Crabtree, R.H., J. Chem. Soc., Dalton Trans., 2001,
0
0.5
1.0
1.5
2.0
2.5
Time, h
p. 2437.
5. Chepaikin, E.G., Kinet. Katal., 2004, vol. 45, p. 331
1
Isobutane oxidation (according to H NMRꢀspectroscopic
[Kinet. Catal. (Engl. Transl.), vol. 45, p. 307].
data) with the formation of (
isoꢀPrOD, ( Ac OCH , and (
BuOD. Reaction conditions: [RhCl ] = 2.5
1
) HCOOD, (
2) Ac OꢀisoꢀPr +
f
6. Stolyarov, I.P., Vargaftik, M.N., Shishkin, D.I., and
Moiseev, I.I., J. Chem. Soc., Chem. Commun., 1991,
no. 14, p. 938.
3)
4
)
Ac O
ꢀisoꢀBu + isoꢀ
f
3
f
–3
×
10 mol/l;
3
reaction medium, CF COOD–D O, mD O = 0.6; temꢀ
7. Lin, M., Hogan, T., and Sen, A., J. Am. Chem. Soc.
1996, vol. 118, p. 4574.
8. Gekhman, A.E., Stolyarov, I.P., Ershova, N.V., Moiseꢀ
eva, N.I., and Moiseev, I.I., Kinet. Katal., 2004, vol. 45,
p. 45 [Kinet. Catal. (Engl. Transl.), vol. 45, p. 40].
,
3
2
2
–3
perature, 95°C; [NaCl] = 7.5
5
× 10 mol/l; [Cu(II)] =
–2
3
× 10 mol/l; isoꢀBuH volume, 285 cm ; O , CO, and
2
He pressures, 0.56, 1.84, and 4.0 MPa, respectively. The
buildup curve of acetone is not shown because a broadened
1
9. Shilov, A.E., Metal Complexes in Biomimetic Chemical
Reactions, New York: CRC, 1997.
H NMR signal is difficult to integrate.
10. Chepaikin, E.G., Boiko, G.N., Bezruchenko, A.P.,
Leshcheva, A.A., and Grigoryan, E.A., Dokl. Akad.
Nauk, 1997, vol. 353, p. 217 [Dokl. Phys. Chem. (Engl.
Transl.), vol. 353, p. 120].
11. Chepaikin, E.G., Bezruchenko, A.P., Leshcheva, A.A.,
Boyko, G.N., Kuzmenkov, I.V., Grigoryan, E.H., and
Shilov, A.E., J. Mol. Catal. A.: Chem., 2001, vol. 169,
p. 89.
12. Chepaikin, E.G., Bezruchenko, A.P., Leshcheva, A.A.,
and Grigoryan, E.A., Dokl. Akad. Nauk, 2000, vol. 373,
p. 66 [Dokl. Phys. Chem. (Engl. Transl.), vol. 373,
p. 105].
13. Chepaikin, E.G., Bezruchenko, A.P., and Leshcheꢀ
va, A.A., Kinet. Katal., 2002, vol. 43, p. 550 [Kinet.
Catal. (Engl. Transl.), vol. 43, p. 507].
in the case of alkanes. For example, acetone is oxiꢀ
dized to HCOOH, CF3COOCH3, and CH3COOH
and propionic acid is oxidized to HCOOH,
CF3COOCH3, CF3COOC2H5, and CH3COOH
,
.
Therefore, it is likely that reaction paths with the conꢀ
secutive oxidation of alkanes into products with shortꢀ
ened chains through alcohols, ketones, and acids can
occur.
Thus, in this work, we found that oxygenates with a
shortened hydrocarbon chain are formed under mild
conditions upon the oxidation of С2–С4 alkanes in the
presence of the Rh/Cu/Cl– catalytic system under the
action of molecular oxygen and carbon monoxide
along with the expected products of substitution for
hydrogen atom (alcohols, ketones, and acids).
14. Chepaikin, E.G., Bezruchenko, A.P., Boiko, G.N, and
Leshcheva, A.A., Neftekhimiya, 2003, vol. 43, p. 434
[Pet. Chem. (Engl. Transl.), vol. 43, p. 395].
15. Chepaikin, E.G., Bezruchenko, A.P., Boiko, G.N.,
Gekhman, A.E., and Moiseev, I.I., Kinet. Katal., 2006,
vol. 47, p. 16 [Kinet. Catal. (Engl. Transl.), vol. 47,
p. 12].
The results of a systematic study of the reactivity of
C–C bonds in structurally different saturated hydroꢀ
carbons in the presence of the developed catalytic sysꢀ
tems will be published elsewhere.
16. Bales, B.C., Brawn, P., Donestani, A., and Mayer, J.M.,
J. Am. Chem. Soc., 2005, vol. 127, p. 2832.
KINETICS AND CATALYSIS Vol. 51
No. 5
2010