1442
Scheme 2.
Acknowledgements
This work was supported by the Ministry of Education, Science, Sports and Culture of Japan (No.
07CE2004).
References
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11. Venturello reported that heating a mixture of octanal and 40% H2O2 (1:1.2 mol ratio) at 90°C for 1 h gave octanoic acid
with a yield of 34%, while the presence of 0.5% [CH3(n-C8H17)3N]3PO4[W(O)(O2)2]4 increased the yield to 87%.4a
12. When a mixture of [CH3(n-C8H17)3N]HSO4 (0.3 mmol), toluene (10 mL), and water (10 mL) in a 20 mm diameter test tube
was mechanically stirred at 1000 rpm for 2 h at room temperature and then allowed to stand for 1 h, the acid was partitioned
1
in toluene and water in a ratio of about 7:3. No concentration gradient was seen in both organic and aqueous phases. H
NMR analysis showed that 1 mL of D2O dissolves 0.068 mmol of [CH3(n-C8H17)3N]HSO4 at 25°C.
13. Typical procedure: A 500 mL, round-bottomed flask equipped with a magnetic stirring bar and a reflux condenser was
charged with 1.82 g (3.90 mmol) of [CH3(n-C8H17)3N]HSO4 and 133 g (1.17 mol) of aqueous 30% H2O2. The mixture was
vigorously stirred at room temperature for 10 min, and then 100 g (780 mmol) of octanal was added. The biphasic mixture
was heated at 90°C with stirring at 1000 rpm for 2 h and then cooled to room temperature. The organic phase was separated,
washed with 100 mL of saturated aqueous Na2S2O3, and distilled through a short column to give 91.5 g (81%) of octanoic
acid as a colorless liquid, b.p. 114.0–116.0°C/3 mmHg.
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Hashimoto, T.; Noyori, R. J. Org. Chem. 1996, 61, 8310–8311. (b) Sato, K.; Aoki, M.; Ogawa, M.; Hashimoto, T.; Panyella,
D.; Noyori, R. Bull. Chem. Soc. Jpn. 1997, 70, 905–915.