Steel-Promoted Oxidation of Olefins
2011±2015
Oxidation of propene in scCO2: 2-Methyl-propionaldehyde (8.20 mmol)
was placed in the 100-mL stainless steel autoclave under a propene
atmosphere (100 mL 4.10 mmol). The reactor was filled with CO2 (75 g,
d 0.75 g mLÀ1) using a compressor. Then dioxygen (ca. 40.0 mmol) was
introduced from a pressurized vessel as described above. After stirring the
mixture for 18 h at 558C (p0tot ꢀ 190 bar) the reactor was vented through a
cryo trap filled with 70 mL of dry and degassed toluene at À508C. The
reactor was washed with toluene and the combined toluene solutions were
analyzed by GC and GC/MS. The yield of oxidation products was
determined using n-heptane as an internal standard and are based on
corrected GC values for all oxidation products.
[3] W. Leitner, Topics in Current Chemistry 1999, 206, 107 ± 132.
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[12] Preliminary results were reported in form of a conference poster: W.
Leitner, F. Loeker in Proceedings of the 6th Meeting on Supercritical
Fluids, Nottingham, April 10 ± 13, 1999, pp. 233 ± 234.
[13] To exclude the possibility of catalysis by trace amounts of metals
remaining in the autoclave from previous experiments, the reactor was
washed extensively with acids, bases, and various organic solvents but
no significant change in epoxidation rate was observed. Finally, we
decided to manifacture a new autoclave from austenitic steel (material
number 1.4571). Again almost quantitative epoxidation of cis-cyclo-
octene occurred in the first run.
Oxidation of olefins in toluene: A 100-mL two-necked round-bottom flask
or the 100-mL stainless steel autoclave described above was charged with
dry and degassed toluene (70 mL), the olefin (2.50 mmol), and 2-methyl-
propionaldehyde (5.00 mmol) under argon. The reaction compartment was
purged with O2 and a gas burette filled with dioxygen was connected. The
reaction mixture was agitated with a magnetic stir bar for 18 h at 558C.
After cooling to ambient temperature the solution was analyzed by GC and
GC/MS.
Epoxidation of cyclohexene in CH2Cl2:[10b] A 50-mL two-necked pear-
shaped flask was charged with dry and degassed CH2Cl2 (10 mL), cyclo-
hexene (2.00 mmol), and 2-methyl-propionaldehyde (6.00 mmol) under
argon. The reaction compartment was purged with O2 and a gas burette
filled with dioxygen was connected. The reaction mixture was agitated with
a magnetic stir bar for 15 h at ambient temperature (23 ± 248C). Then the
solution was analyzed by GC and GC/MS.
Acknowledgement
This work was supported by the Max-Planck-Society, the Deutsche
Forschungsgemeinschaft (Gerhard-Hess-Programm), the Government of
North-Rhine-Westphalia (Bennigsen-Foerder-Programm), and the Fonds
der Chemischen Industrie.
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Nottingham, April 10 ± 13, 1999, p. 349; b) G. J. Suppes, R. N. Oc-
chiogrosso, M. A. McHugh, Ind. Eng. Chem. Res. 1989, 28, 1152 ±
1156.
[15] This induction period shows some variation, see Table 1, entry 3.
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Wai, Talanta 1997, 44, 137 ± 150.
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Received: October 8, 1999 [F2074]
Chem. Eur. J. 2000, 6, No. 11
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