1
288
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Kapustina et al.
a Perkin—Elmer 577 spectrophotometer. The H and 13C NMR
spectra were recorded on a Bruker ACꢀ200 instrument in CDCl3.
The GCꢀMS analysis was performed on a Finigan MAT ITDꢀ700
spectrometer (EI, 70 eV, the source of ion—ionic trap system
temperature was 220 °C) connected with Carlo Erba 4200 chroꢀ
matograph with a 0.2×2500 mm Ultraꢀ1 column (Hewlett—Pacꢀ
kard), the stationary phase (polymethylsiloxane) thickness
1
2. M. P. Doyle, L. J. Zuidema, T. R. Bade, J. Org. Chem., 1975,
40, 1454.
3. L. B. Young, W. S. Trahanovsky, J. Org. Chem., 1967,
32, 2349.
4. W. S. Trahanovsky, L. B. Young, G. L. Brown, J. Org. Chem.,
1967, 32, 3865; W. S. Trahanovsky, L. B. Young, J. Chem.
Soc., 1965, 5777.
0
.33 μm, helium was used as a carrier gas. The reaction products
5. W. S. Trahanovsky, in Methods in FreeꢀRadical Chemistry,
Ed. E. S. Huyser, Marcel Dekker, New York, 1973, 4, 133.
6. H. Z. Hintz, D. C. Johnson, J. Org. Chem., 1967, 32, 556.
7. S. E. Schaafsma, H. Steinberg, T. J. de Boer, Recl. Trav.
Chim. PayꢀB, 1966, 85, 73; K. Meyer, J. Rocek, J. Am. Chem.
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Soc., 1969, 91, 5068.
9. N. I. Kapustina, L. L. Sokova, R. G. Gasanov, G. I. Niꢀ
kishin, Izv. Akad. Nauk, Ser. Khim., 2007, 1445 [Russ. Chem.
Bull., Int. Ed., 2007, 56, 1501].
were isolated by column chromatography (silica gel, L 40×100 μm,
eluent — heptane—ethyl acetate). The starting primary alcohols
(
hexanꢀ1ꢀol (1a), heptanꢀ1ꢀol (1b), nonanꢀ1ꢀol (1c)) and secꢀ
ondary alcohols (pentanꢀ3ꢀol (3a), nonanꢀ5ꢀol (3b), 2,4ꢀdiꢀ
methylpentanꢀ3ꢀol (3c)) (Acros) were distilled prior to use.
Cerium(III) nitrate (Ce(NO ) •6H O) of 99.5% purity (Acros)
was used as purchased. Lithium bromide, sodium bromide, and
potassium bromide were dried in the oven prior to use. Acetoniꢀ
trile (pure grade, Acros) was distilled before use.
3
3
2
Oxidation of primary alkanols with a Ce(NO ) •6H O—
3
3
2
LiBr—H O system (general procedure). A solution of hydrogen
10. G. I. Nikishin, L. L. Sokova, N. I. Kapustina, Izv. Akad.
Nauk, Ser. Khim., 2010, 383 [Russ. Chem. Bull., Int. Ed.,
2010, 59, 391].
11. J. Jiao, L. X. Ngugen, D. R. Patteson, R. A. Flowers, Org.
Lett., 2007, 9, 1323.
12. T.ꢀL. Ho, Synthesis, 1978, 936.
13. H. Tomioka, K. Oshima, H. Nozaki, Tetrahedron Lett., 1982,
23, 539.
2
2
peroxide (35% solution) in water (10 mL) was added portionwise
20—25 portions of 0.4—0.5 mL) at 65—70 °C to a vigorously
(
III
stirred solution of primary alkanol 1a—c (1 mmol), Ce nitrate
and LiBr in water (10 mL) (ratio of reagents are given in Tables 1
and 2). After addition of the first portion of hydrogen peroxide
solution, a yellow color of the reaction mixture characteristic of
IV
Ce salts was observed, next portion of the hydrogen peroxide
solution was added only after the color completely disappeared.
Then the reaction mixture was cooled, extracted with diethyl
ether (3×15 mL), the combined organic phase was washed with
14. T.ꢀL. Ho, Synth. Commun., 1979, 9, 237.
15. M. H. Ali, D. Kriedelbaugh, T. Wencewicz, Synthesis,
2007, 3507.
water, and dried with MgSO . After removal of the solvent
in vacuo, the yield of products 2a—c and conversion of alkanols
16. G. A. Olah, B. G. B. Gupta, A. Funy, Synthesis, 1980, 897.
17. S. S. Kim, H. C. Jung, Synthesis, 2003, 2135.
18. J. Christoffers, T. Werner, S. Unger, W. Frey, Eur. J. Org.
Chem., 2003, 425; J. Christoffers, T. Werner, W. Frey,
A. Baro, Eur. J. Org. Chem., 2003, 4879; J. Christoffers,
T. Kauf, T. Werner, M. Rössle, Eur. J. Org. Chem., 2006, 2601.
19. F. J. MorenoꢀDorado, F. M. Guerra, F. L. Manzano, F. J.
Aladro, Z. D. Jorge, G. M. Massanet, Tetrahedron Lett.,
2003, 44, 6691.
4
1
a—c were determined by GC using internal standard. The prodꢀ
ucts were isolated by column chromatography on silica gel.
Oxidation of secondary alkanols with a Ce(NO ) •6H O—
3
3
2
LiBr—H O system (general procedure). A solution of hydrogen
2
2
peroxide (35% solution) in water (10 mL) was added portionwise
20—25 portions of 0.4—0.5 mL) at 65—70 °C to a vigorously
(
III
stirred solution of secondary alkanol 3a—c (1 mmol), Ce nitrate
and LiBr in 80% aqueous MeCN (10 mL) (ratio of reagents are
given in Table 3). The products were isolated as described above.
20. G. I. Nikishin, L. L. Sokova, N. I. Kapustina, Izv. Akad.
Nauk, Ser. Khim., 2009, 2325 [Russ. Chem. Bull., Int. Ed.,
2
009, 58, 2402].
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 09ꢀ03ꢀ00292a).
21. G. I. Nikishin, L. L. Sokova, N. I. Kapustina, Izv. Akad.
Nauk, Ser. Khim., 2009, 303 [Russ. Chem. Bull., Int. Ed.,
2
009, 58, 303].
References
1
. W. S. Trahanovsky, L. B. J. Young, P. M. Nave, Tetrahedron
Lett., 1969, 30, 2501.
Received April 01, 2010