MeOH formed). The concentration of formaldehyde was measured
spectrophotometrically after its transformation into 2,6-dimethyl-3,5-diace-
tyl-1,4-dihydropyridine as described previously.4b
‡ The reaction was carried out in a glass tube placed into the stainless steel
autoclave (100 ml, volume of the solution = 10 ml). (CAUTION: the
Table 3 Carboxylation of methane by carbon monoxide in the presence of
a
H O
2 2
catalysed by NaVO
3
and PCA in aqueous solution
3
Products (concentration/10
23
mol dm
)
2 2
combination of air and H O with organic compounds at elevated pressures
Pressure CO/bar T/ °C
5 25
t/h
MeCO
2
H
MeOOH
and temperatures may be explosive!). The resulting solution was analysed
by GC (the concentration of MeOOH was measured as concentration of
4
2
8
0.9
1.1
1.3
1.6
0.0
0.0
0.0
0.0
MeOH after reduction of the solution with sodium tetrahydroborate ), as
1
well as by GC–MS and H NMR.
1
4
6
8
1 Recent reviews: A. E. Shilov and G. B. Shul’pin, Chem. Rev., 1997, 97,
2
879; Y. Fujiwara, K. Takaki and Y. Taniguchi, Synlett, 1996, 591; R. H.
4
6
0
0
2
4
8
6
8
1.1
1.3
1.7
1.8
1.9
0.8
1.4
1.7
2.1
2.6
Crabtree, Chem. Rev., 1995, 95, 987. Recent original papers: R. A.
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1
4
2
4
7
6
0.4
0.5
0.5
0.5
0.9
1.6
2.3
2.8
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1
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30
25
2
4
8
6
0
0.4
0.7
0.9
1.1
1.6
0.0
0.0
0.0
0.0
0.0
1
5
4
0
2
4
8
6
0
0.5
0.8
1.2
1.4
2.2
0.0
0.0
0.0
0.0
0.0
1
5
4
51; K. Wada, M. Nakashita, A. Yamamoto and T. Mitsudo, Chem.
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a
Conditions, see Footnote ‡. Pressures and concentrations: CH
4
, 50 bar;
23
24
23
24
H
2 2 3
O , 0.1 mol dm ; NaVO , 1.0 3 10 mol dm ; PCA, 4.0 3 10
23
24
mol dm . Value 0.0 means below detection limit (0.5 3 10
mol dm23).
2
radicals (dry CO reforming of methane in the presence of solid
3
(a) P. Margl, T. Ziegler and P. E. Bl o¨ chl, J. Am. Chem. Soc., 1996, 118,
412; (b) H.-J. Freund, J. Wambach, O. Seiferth and B. Dillmann, Ger.
7
catalyst at high temperatures is well-known process ).
We thank BASF, the Russian Basic Research Foundation,
and the Swiss National Science Foundation for support. Authors
are indebted to Dr Arthur H o¨ hn, Dr Michael Slany (BASF AG,
Ludwigshafen, Germany) and Dr Yuriy N. Kozlov (Institute of
Chemical Physics, Moscow) for fruitful discussions.
5
Pat. DE 44 28 566 C1 (to Hoechst A.G.) 1995.
4
G. B. Shul’pin, D. Attanasio and L. Suber, J. Catal., 1993, 142, 147;
G. V. Nizova and G. B. Shul’pin, Russ. Chem. Bull., 1994, 43, 1146;
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52, 13 051; G. V. Nizova, G. S u¨ ss-Fink and G. B. Shul’pin, Chem.
Commun., 1997, 397; Tetrahedron, 1997, 53, 3603; G. S u¨ ss-Fink, G. V.
Nizova, S. Stanislas and G. B. Shul’pin, J. Mol. Catal. A, 1998, 130,
Notes and References
1
63.
†
The oxidations were carried out in a stainless steel autoclave with
5 M. M. Kats and G. B. Shul’pin, Bull. Acad. Sci. USSR, Div. Chem. Sci.,
1990, 39, 2233.
intensive stirring (volume of the reaction solution = 30 ml and total volume
of autoclave = 100 ml). The autoclave was charged with synthetic air (78%
6 K. Nagahara, I. Ryu, N. Kambe, M. Komatsu and N. Sonoda, J. Org.
Chem., 1995, 60, 7384; A. P. E. York, J. B. Claridge, A. J. Brungs, S. C.
Tsang and M. L. H. Green, Chem. Commun., 1997, 39; J. H. Bitter, K.
Seshan and J. A. Lercher, J. Catal., 1997, 171, 279; Y. Lu, J. Xue, Y. Liu
and S. Shen, Chem. Lett., 1997, 515; U. Olsbye, T. Wurzel and L.
Mleczko, Ind. Eng. Chem. Res., 1997, 36, 5180; M. C. J. Bradford and
M. A. Vannice, J. Catal., 1998, 173, 157.
N
2
, 21% O
to the appropriate pressures. The reactions were stopped by cooling with ice,
and the reaction solution was analysed for MeCO H and MeOH by GC
DANI-86.10; fused silica capillary column 25 m 3 0.32 mm 3 0.25 mm,
CP-WAX52CB; integrator SP-4400), as well as by GC–MS (NERMAG R
0-10, capillary column 25 m 3 0.32 mm 3 0.25 mm, CP-WAX52CB) and
2
, 1% Ar), and consecutively with carbon monoxide and methane
2
(
3
1
H NMR (Varian spectrometer, 200 MHz; in D
2
O; in this case GC–MS
H and
analysis testified partial H–D exchange in methyl groups of MeCO
2
Received in Cambridge, UK, 22nd June 1998; 8/04699I
1886
Chem. Commun., 1998