3
084
A. V. Bekish / Tetrahedron Letters 53 (2012) 3082–3085
Table 2
Contents of
a
-C–C-bond cleavage by-products on the oxidation of 8-bromooctan-1-ol (2) and decan-1-ol (3) with the Jones reagent in the presence of various additives
Entry
Substrate
Conditionsa
By-product contentb (%)
Temperature
Additive (equiv. per mol of substrate)
Method
1
2
3
4
5
6
7
8
9
3
3
2
3
3
3
3
3
3
3
3
3
0 °C
55 °C
0 °C
0 °C
0 °C
55 °C
55 °C
55 °C
55 °C
0 °C
H
H
H
H
H
H
Ce(NO
(NH
Ce(SO
2
2
2
2
2
2
C
C
C
C
C
C
2
2
2
2
2
2
O
O
O
O
O
O
4
4
4
4
4
4
Á2H
Á2H
Á2H
Á2H
Á2H
Á2H
2
2
2
2
2
2
O (4 equiv)
O (4 equiv)
O (3 equiv)
O (3 equiv)
O (12.5 equiv)
O (3 equiv)
A
A
B
B
B
B
A
C
C
B
D
D
4.5
1.5
2.7
1.7
0.7
1.3
1.3
1.2
1.2
1.0
2.0
1.0
3
)
3
Á6H
Ce(NO
O (0.1 equiv)
2
O (0.2 equiv)
)
4 2
3 6
) (0.1 equiv)
4
)
2
Á4H
2
10
11
12
(NH
(NH
(NH
)
4 2
)
4 2
)
4 2
Ce(NO
Ce(NO
Ce(NO
)
3 6
)
3 6
)
3 6
(0.1 equiv)
(0.04 equiv)
(0.5 equiv)
0 °C
0 °C
a
Conditions: (A) A solution of alcohol (0.2 g) and the corresponding amount of additive in acetone (2 mL) was added dropwise over 30 min to a stirred solution of 8 N Jones
reagent (3.5 mL). For entry 7, 2 mL of Jones reagent and acetone containing 10 vol% of water (2 mL) were used. (B) 8 N Jones reagent (2 mL) was added dropwise over 10-
1
5 min to a stirred solution of alcohol (0.2 g) and additive in acetone (2 mL). For entry 5, Jones reagent (2.5 mL) and 15 mL of acetone were used. (C) A solution of alcohol
(
0.2 g) in acetone (2 mL) was added dropwise over 30 min to a stirred solution of 8 N Jones reagent (2 mL) containing the additive. (D) 8 N Jones reagent (1.2 mL)
containing the additive was added dropwise over 30 min to a stirred solution of the alcohol (0.2 g) in acetone (2 mL).
According to GC–MS analysis of the corresponding methyl ester.
b
22
Table 3
Contents of
a-C–C-bond fission by-products on the oxidation of 8-bromooctan-1-ol (2) and decan-1-ol (3) with different oxidants
Entry
Substrate
Oxidant
Temperaturea
By-product contentb (%)
1
2
3
4
5
6
7
8
9
2
2
2
2
2
2
3
3
3
KMnO
KMnO
4
/H
2
SO
4
50 °C
50 °C
20 °C
100 °C
20 °C
0 °C
100 °C
20 °C
0 °C
3.1
7.0
2.6
60
0.3
0.4
37
4
/NaOH
NiCl
HNO
TEMPO/PhI(OAc)
2
/NaClO
3
2
2
H
5
IO
/CrO
6 3
HNO
3
TEMPO/PhI(OAc)
IO /CrO
0.2
0.4
H
5
6
3
a
For other reaction conditions see Ref.3–9
According to GC–MS analysis of the corresponding methyl ester.
b
22
carboxylic acid containing one carbon atom less than the major
product. In the case of nitric acid as the oxidant, besides the impu-
rity mentioned above, the product also contained significant
8. Ho, T.-L.; Hall, T. W. Synth. Commun. 1975, 5, 309.
(a) Anelli, P. L.; Biffi, C.; Montanari, F.; Quici, S. J. Org. Chem. 1987, 52, 2559;
b) De Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.; Piancatelli, G. J. Org.
9.
(
Chem. 1997, 62, 6974; (c) Epp, J. B.; Widlanski, Th. S. J. Org. Chem. 1999, 64,
293.
2
6
amounts of a carboxylic acid with two less carbon atoms.
10. Hill, Sh.; Hirano, K.; Shmanai, V. V.; Marbois, B. N.; Vidovic, D.; Bekish, A. V.;
Temperature, the order of reagent addition, and additives such
as oxalic acid or cerium salts produced a profound effect on the
formation of the undesired impurity during the Jones oxidation
Kay, B.; Tse, V.; Fine, J.; Clarke, C. F.; Shchepinov, M. S. Free Radical Biol. Med.
2011, 50, 130.
11. Meyer, M. P.; Klinman, J. P. Tetrahedron Lett. 2008, 49, 3600.
1
2. This was proved by gas chromatography-mass spectrometry (GC–MS) using a
Hewlett Packard GCMS 5890/5972 (HP Innovax capillary column,
length = 50 m, diameter = 0.2 mm, electron impact energy = 70 eV). The
carboxylic acids were transformed into the corresponding methyl esters
of unbranched primary alcohols. The application of H
5 6 3
IO /CrO or
TEMPO/PhI(OAc) provided acids with minimum contents of
2
impurities formed due to carbon skeleton degradation. These facts
are important for the synthesis of biologically active compounds of
11
using CH
hydrogenated [H2-Pd(OH)2/C] to form methyl decanoate to perform an
alternative analysis (with commercially available methyl nonanoate as
3 2
OH/H SO
4
before analysis. Methyl dec-9-ynoate was also
2
7
high purity.
a
control). The presence of methyl nonanoate (detected using commercial
methyl nonanoate as the control) in the methyl decanoate thus obtained
additionally confirmed the presence of methyl non-8-ynoate in methyl dec-9-
ynoate.
Acknowledgement
This work was supported by the Belarusian State University.
13. (a) Tojo, G.; Fernandez, M. Basic Reactions in Organic Synthesis. Oxidation of
Primary Alcohols to Carboxylic Acids. A Guide to Current Common Practice;
Springer, 2007; (b) Trost, B. M.; Fleming, I. In Comprehensive Organic Synthesis
Selectivity Strategy and Efficiency in Modern Organic Chemistry; Pergamon Press,
References and notes
2
007; vol. 7,; (c) Hudlicky, M Oxidations in Organic Chemistry; ACS Monograph
1
.
.
Larock, R. C. Comprehensive Organic Transformations; Wiley: New York, 1999.
pp. 1646–1650.
(a) Bowden, K.; Heilbron, I. M.; Jones, E. R. H.; Weedon, B. C. L. J. Chem. Soc.
186, 1990.
14. In contrast, there are numerous examples of the formation of carbon–carbon
bond fission products on Cr(VI) oxidation of 1,2-glycols and secondary and
tertiary alcohols.1
15. (a) Tojo, G.; Fernandez, M. Basic Reactions in Organic Synthesis. Oxidation of
Alcohols to Aldehydes and Ketones. A Guide to Current Common Practice; Springer,
2006. pp. 12–17, 38–43, 69–71; (b) Mosher, W. A.; Whitmore, F. C. J. Am. Chem.
Soc. 1948, 70, 2544; (c) Mosher, W. A.; Langerak, E. O. J. Am. Chem. Soc. 1951, 73,
1302; (d) Muller, P.; Blanc, J. Helv. Chim. Acta 1980, 1979, 62.
16. Just, G.; Luthe, C.; Oh, H.; Montgomery, J. Synth. Commun. 1979, 9, 613.
17. Several specific examples have been described where the oxidation of
2
3,15
1
1
946, 39; (b) Heilbron, I.; Jones, E. R. H.; Sondheimer, F. J. Chem. Soc. 1947,
586; (c) Heilbron, I.; Jones, E. R. H.; Sondheimer, F. J. Chem. Soc. 1949, 604.
3
.
(a) Degering, E. F.; Boatright, L. G. J. Am. Chem. Soc. 1950, 72, 5137; (b) Lynch, K.
M.; Dailey, W. P. J. Org. Chem. 1995, 60, 4666.
Pattison, F. L. M.; Stothers, J. B.; Woolford, R. G. J. Am. Chem. Soc. 1956, 78, 2255.
Corey, E. J.; Schmidt, G. Tetrahedron Lett. 1979, 20, 399.
Zhao, M.; Li, J.; Song, Zh.; Desmond, R.; Tschaen, D. M.; Grabowski, E. J. J.;
Reider, P. J. Tetrahedron Lett. 1998, 39, 5323.
4
5
6
.
.
.
7
.
(a) Crombie, L.; Harper, S. H. J. Chem. Soc. 1950, 2685; (b) Billman, J. H.; Parker, E.
E. J. Am. Chem. Soc. 1944, 66, 538; (c) Kenyon, J.; Platt, B. C. J. Chem. Soc. 1939, 633.
functionalized primary alcohols involved heterolytic cleavage of not only C–
H but also C–C bonds.1
3a,18
However, the unusual C–C bond cleavage in these