274
T. Hida, H. Nogusa / Tetrahedron 65 (2009) 270–274
(m, 2H), 4.44–4.55 (tt,1H). 13C NMR (150 MHz, CDCl3,
d
) 11.35,11.43,
generation of acetone was detected by GC (yield: 24%). GC (FID):
m (J&W Scientific); carrier gas,
helium 1.0 mL/min; column temperature, 35 ꢀC, 5 min; final tem-
perature, 100 ꢀC; progress rate, 15 ꢀC/min; injection temperature,
200 ꢀC; detector temperature, 250 ꢀC; split ratio, 20:1; tR of ace-
tone, 3.0 min; tR of 2-propanol, 3.2 min.
13.47, 13.50, 16.17, 16.91, 18.68, 18.97, 20.90, 20.97, 24.88, 24.97,
29.97, 30.05, 43.812, 44.16, 52.46, 52.72, 60.72, 61.24, 67.27, 67.52,
97.29, 98.20, 212.21, 212.94. HRMS (FABþ) calcd for C13H25O3:
([MþH]þ), 229.1804; found (m/z): 229.1797.
column, DB-1 0.25 mmꢁ30 m, 1.0
m
4.7. Oxidation of 2-ethyl-1-hexanol
Acknowledgements
A solution of 3.26 g (25.0 mmol) of 2-ethyl-1-hexanol in 50 mL
of DMA was heated to 90 ꢀC, and a cold mixture of 2.78 g
(27.4 mmol) of 35% H2O2, 0.36 g (1.0 mmol) of Na2HPO4$12H2O, and
82.5 mg (0.25 mmol) of Na2WO4$2H2O was added dropwise. The
reaction was continued at 90 ꢀC for 4 h. The yield of 2-ethyl-1-
hexanal was determined by GC. After the reaction 50 mL of toluene
and 50 g of 10% brine including Na2SO3 were added to the reaction
mixture. The organic layer was separated and washed with 10%
brine. The aqueous layer was extracted with 50 mL of toluene. The
organic layers were combined and condensed under reduced
pressure at 40 ꢀC. Into the residue, 30 g of 10% disodium carbonate
solution and 30 mL of toluene were added and the aqueous layer
was separated. Into the aqueous layer 62% sulfulic acid and 50 mL of
toluene were added. The organic layer was separated and con-
densed under reduced pressure at 40 ꢀC. The residue (1.08 g) was
identified by NMR compared with authentic 2-ethyl-hexanoic acid.
The structure determination of Na2[W(O2)4]$2H2O by X-ray
analysis for single crystal was done by Mr. Hiroshi Nakai and Ms.
Yuuko Fujimura in Shionogi Research Laboratories. And we thank
Professor Tetsuo Ohta in Doshisha University, Dr. Yoshitaka Araki
and Dr. Toshiro Konoike in Shionogi CMC Development Laborato-
ries for helpful discussions.
Supplementary data
Supplementary data associated with this article can be found in
References and notes
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GC condition (FID): column, DB-WAX 0.25 mmꢁ30 m, 0.25
mm;
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4.8. Preparation of Na2[W(O2)4]$2H2O
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A solution of 2.15 g (6.52 mmol) of Na2WO4$2H2O and 18.0 g
(158.8 mmol) of 30% H2O2 was added into 80 mL of DMA at room
temperature, followed by stirring for a few minutes. Yellow crystals
of Na2W(O2)4$2H2O were obtained by filtration (2.07 g,
5.95 mmol). Single crystal of Na2[W(O2)4]$2H2O was obtained from
a solution of 107.72 mg (0.33 mmol) of Na2WO4$2H2O, 0.76 g
(7.71 mmol) of 35% H2O2, and 7 mL of DMA, which were left in
a refrigerator (5 ꢀC) for 2 days. The structure was determined by
X-ray analysis.
4.9. Oxidation of 2-propanol using Na2[W(O2)4]$2H2O
Into 30 mL of DMA or water, 70.2 mg (1.16 mmol) of 2-propanol
and 101.6 mg (0.29 mmol) of Na2[W(O2)4]$2H2O were dissolved.
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