Reagent for the oxidation of secondary alcohols
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1067
Table 1. Reaction conditions and the yields and physicochemical data of the compounds obtained
Compound
Reaction conditions
Yield
%)
B.p./°C (p/Torr)
or [m.p./°C]a
IR,
ν/cm–1
13C NMR,
δ
(
T/°C
t/h
Acetone (2a)
Acetophenone (2b)
200
200
1
3
93
83
56 {56.2}12
99 (35) {202.3}12
1712 (C=O)
1720 (C=O)
30.7 (Me); 206.7 (C=O)
137.4 (C(1), Ph);
1
1
1
28.6 (C(2), C(6), Ph);
28.4 (C(3), C(5), Ph);
32.9 (C(4), Ph); 196.9
(
C=O); 25.7 (Me)
10.3 (C(1), C(2),
cycloꢀC H ); 21.2 (C(3),
Acetylcyclopropane (2c)
200
200
1
3
82
90
114—115 {114}12
1715 (C=O)
3
5
cycloꢀC H ); 208.0 (C=O);
3
5
2
9.9 (Me)
1
ꢀAcetyladamantane (2d)
[53—53.5] {53—55}12 1704 (C=O)
45.7 (C(1)); 37.4 (C(2),
C(8), C(9));
2
3
2
7.2 (C(3), C(5), C(7));
6.1 (C(4), C(6), C(10));
10.2 (C=O); 24.1 (Me)
Cyclopentanone (3a)
Cyclohexanone (3b)
Cycloheptanone (3c)
Cyclooctanone (3d)
Adamantanꢀ2ꢀone (6)b
200
200
200
200
200
3
3
3
3
3
84
85
83
83
90
130—131 {130}12
—
—
—
—
—
219.6 (C=O)
219.8 (C=O)
213.9 (C=O)
216.7 (C=O)
216.7 (C(2), C=O)
1
2
46.5 (15) {155.6}
75 (20) {179}12
78 (20) {195—197}12
[256—257] (subl.)
{
256—258}14
Camphor (8)c
Cholestꢀ5ꢀenꢀ3ꢀone (10)
200
200
3
3
90
80
12
15
[177—178] {178.5}
[118.5—119] {119}
1730 (C=O)
1730 (C=O)
217.5 (C(2), C=O)
205.0 (C=O)
d
a
The literature data are given in braces.
b
c
Found (%): C, 79.61; H, 9.52. C H O. Calculated (%): C, 79.95; H, 9.39.
10
14
Found (%): C, 78.91; H, 10.48. C H O. Calculated (%): C, 78.90; H, 10.59.
10
16
d
Found (%): C, 83.96; H, 11.89. C H O. Calculated (%): C, 84.31; H, 11.53.
2
7
44
Manganese compounds (MnCl , MnSO , Mn(OAc) , and
2. J. A. Cella, J. A. Kelley, and E. F. Kenehan, J. Org. Chem.,
1975, 40, 1860.
2
4
2
Mn(C H CO ) ) were preliminarily recrystallized and dried
1
7
35
2 2
in a vacuum desiccator; Mn(acac) was prepared as described
in Ref. 11 and dried in vacuo (20 h, 80 °C).
Oxidation of secondary alcohols (general procedure). Mangaꢀ
nese tris(acetylacetonate) (0.1 mmol), MeCN (0.2—0.4 mmol),
a corresponding secondary alcohol (10—20 mmol), and CCl4
3. B. J. Ganem, J. Org. Chem., 1975, 40, 1998.
4. T. Miyazawa and T. Endo, J. Mon. Catal., 1985, 82, 357.
5. A. H. Haines, Methods for the Oxidation of Organic Comꢀ
pounds, Academic Press, New York, 1985.
6. P. L. Anelli, S. Banfi, F. Montanari, and S. Quici, J. Org.
Chem., 1989, 54, 2970.
3
(
20—50 mmol) were placed in a glass tube or a steel microꢀ
autoclave (V = 17 mL) (in an atmosphere of argon). The tube
was sealed (or the microautoclave was hermetically closed).
The reactions mixtures were stirred at 200 °C for 1—3 h. Then
the tube (autoclave) was cooled to ∼20 °C, and the reaction
mixture was filtered through a silica gel layer with hexane—ether
7. J. Einborn, C. Einborn, F. Ratajczak, and J. L. Pierre,
J. Org. Chem., 1996, 61, 7452.
8. S. D. Rychnovsky and R. Vaidyanthan, J. Org. Chem., 1999,
64, 310.
9. G. Charlot, Les methodes de la chimie analytique, Paris, 1961.
(
1 : 1) as an eluent. The solvent was removed, and the residue
10. Organikum.
Organischꢀchemisches
Grundpraktikum,
was distilled or crystallized from EtOH.
Deutscher Verlag der Wissenschaften, Berlin, 1976.
11. A. P. Borisov, L. A. Petrova, and V. D. Makhaev, Zh. Obshch.
Khim., 1992, 62, 15 [Russ. J. Gen. Chem., 1992, 62 (Engl.
Transl.)].
The structures of the ketones obtained were proved by comꢀ
paring them with the authentic samples and the reference
data.1
2—15
The reaction conditions and the yields and physicoꢀ
chemical properties of the compounds obtained are given in
Table 1.
12. I. T. Goronovskii, Yu. P. Nazarenko, and E. F. Nekryach,
Kratkii spravochnik po khimii [Concise Handbook of Chemisꢀ
try], Naukova Dumka, Kiev, 1974, 992 pp. (in Russian).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ15ꢀ97312).
1
3. R. W. Binkley, Synth. Commun., 1976, 6, 281.
14. H. W. Geluk and J. L. Schlatmann, Tetrahedron, 1968,
4, 5361.
15. A. Howard, Tetrahedron Lett., 1975, 2257.
Received September 4, 2000;
in revised form April 3, 2002
2
References
1
. C. Jrwin and G. Hennion, J. Am. Chem. Soc., 1941, 63, 858.