F. Zimmermann et al. / Tetrahedron Letters 46 (2005) 3201–3203
3203
lead to carboxylic and dicarboxylic acids in relatively
good yields. This oxidation can be performed in a larger
scale with the same reaction times and yields.
U.S. Patent 5,321,158, 1994; Chem. Abstr. 1996, 125,
36578.
11. (a) Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless,
K. B. J. Org. Chem. 1981, 46, 3936–3938; (b) Rossiter, B.
E.; Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1981,
1
2
3
In conclusion, the toxic carbon tetrachloride initially
used in the Sharpless system can be avoided and re-
placed with ethyl acetate in maintaining catalytic ruthe-
nium oxidation. The oxidative cleavage of the C@C
bond of alkenes is accomplished in good yields with
1
03, 464–465.
2. Janssen, L. J. J.; Blijlevens, M. H. A. Electrochim. Acta
003, 48, 3959–3964.
1
1
2
3. B a¨ umer, U.-St.; Sch a¨ fer, H. J. Electrochim. Acta 2003, 48,
489–495.
H O/MeCN/AcOEt solvent system in a ratio 3/2/2 and
2
14. Montreal protocol and Regulation (EC) 2037/00 on
controlled substances that deplete the ozone layer.
this method is efficient especially to produce dicarb-
oxylic acids from monoenic fatty acids. Studies are in
progress in our laboratories to complete this oxidative
system with the regeneration of the oxidants.
1
1
1
5. Shing, T. K. M.; Tam, E. K. W. Tetrahedron Lett. 1999,
0, 2179–2180.
6. The deviations from this solvent ratio led to slower
4
reactions and poorer yields.
7. Solubility of azelaic acid in water at 23 ꢁC is 1.4 g L
solubilities of azelaic and pelargonic acids in warm water
À1
;
Acknowledgements
À1
(
Ref. 6b.
80 ꢁC) are, respectively, 154.4 and 0.6 g L ; detailed in
We are grateful to the ADEME (French Environment
and Energy Management Agency) and Regional council
of Lorraine for financial support.
1
1
2
8. One step of purification gives azelaic acid in 87% yield
with 91% purity (pelargonic acid is the only impurity).
9. The resulting insoluble in water corresponds to pelargonic
acid as colourless oil.
0. Typical procedure: flask is charged with a magnetic
stirred, 3 mL of water, 2 mL of acetonitrile, 2 mL of ethyl
acetate, 282 mg (1 mmol) of oleic acid and 877 mg
(4.1 equiv) of sodium metaperiodate. To this biphasic
solution, 5 mg (2.2 mol %) of ruthenium trichloride
hydrate was added and the entire mixture was stirred
vigorously for 2 h at room temperature. The mixture was
extracted with AcOEt (3 · 10 mL) and the combined
References and notes
1
. (a) Baumann, H.; B u¨ hler, M.; Fochem, H.; Hirsinger, F.;
Zoebelein, H.; Falbe, J. Angew. Chem., Int. Ed. Engl. 1988,
2
7, 41–62; (b) Wightman, P.; Eavis, R.; Batchelor, S.;
Walker, K.; Bennett, R.; Carruthers, P.; Tranter, R. OCL
999, 6, 384–388.
1
2
. Biermann, U.; Friedt, W.; Lang, S.; L u¨ hs, W.; Machm u¨ l-
ler, G.; Metzger, J. O.; Klaas, M. R. gen.; Sch a¨ fer, J.;
Schneider, M. P. Angew. Chem., Int. Ed. 2000, 39, 2206–
organic extracts were dried (MgSO
) and concentrated.
4
The resulting material was purified in warm water.
Pelargonic acid (65%):
1
H
3
NMR (CDCl /TMS,
2224.
. (a) Goebel, C. G.; Brown, A. C.; Oehlschlaeger, H. F.;
Rolfes, R. P. U.S. Patent 2,813,113, 1957; Chem. Abstr.
250 MHz): d 11 (1H, s), 2.3 (2H, t, J = 7.5 Hz), 1.6 (4H,
1
m), 1.3 (8H, m), 0.9 (3H, t, J = 6.1 Hz); C NMR (CDCl
3
3
3
/
TMS): d 180.7, 34.3, 31.9, 29.3, 29.2 (2C), 24.8, 22.7, 14.1;
À1
1
1
958, 52, 2431; (b) Oehlschlaeger, H. F.; Rodenberg, H. G.
U.S. Patent 3,402,108, 1968; Chem. Abstr. 1968, 69,
05917.
FT-IR (CCl
(DMSO-d /TMS, 250 MHz): d 11.9 (1H, s), 2.2 (4H, t,
J = 7.4 Hz), 1.5 (4H, m), 1.2 (6H, m); C NMR (DMSO-
4
): 1712 cm . Azelaic acid (73%): H NMR
6
1
3
1
4. Hill, K. Pure Appl. Chem. 2000, 72, 1255–1264.
5. (a) Rocca, E.; Steinmetz, J. Corros. Sci. 2001, 43, 891–902;
d
6
/TMS): d 174.4 (2C), 33.7 (2C), 28.4 (2C), 28.5, 24.5
À1
(2C); FT-IR (KBr) 1701 cm
.
(
1
b) Muller, B.; F o¨ rster, I.; Kl a¨ ger, W. Prog. Org. Coat.
997, 31, 229–233.
. (a) Peneliau, F.; Meux, E.; Lecuire, J. M. Hydroplus 2002,
28, 90–93; (b) Zimmermann, F.; Meux, E.; Oget, N.;
Lecuire, J. M.; Mieloszynski, J. L. J. Phys. IV France
004, 122, 223–228.
21. All products gave satisfactory spectral data in agreement
with the assigned structure. As example see Ref. 18 for
azelaic and pelargonic acids. For the methyl esters: methyl
6
1
1
nonanoate: H NMR (CDCl
(3H, s), 2.3 (4H, t, J = 7.5 Hz), 1.6 (4H, m), 1.3 (6H, m),
3
/TMS, 250 MHz): d 3.7
1
3
2
3
0.9 (3H, t, J = 6.2 Hz); C NMR (CDCl /TMS): d 174.2,
7
8
. Garti, N.; Avni, E. Colloids Surf. 1982, 4, 33–41.
. (a) Warwel, S.; Klass, M. R. gen. Lipid Technol. 1997, 10–
14; (b) Klass, M. R. gen.; Bavaj, P.; Warwel, S. Fat Sci.
Technol. 1995, 97, 359–367.
51.4, 34.2, 32.0, 29.4, 29.3, 29.2, 25.1, 22.8, 14.1; FT-IR
(CCl ) 1740 cm ; GC–MS (70 eV) m/z: 172 (2), 141 (9),
À1
4
1
87 (41), 74 (100). Dimethyl azelate: H NMR (CDCl
3
/
TMS, 250 MHz): d 3.7 (6H, s), 2.3 (4H, t, J = 7.4 Hz), 1.6
1
3
9
. (a) Santacesaria, E.; Sorrentino, A.; Rainone, F.; Di Serio,
M.; Speranza, F. Ind. Eng. Chem. Res. 2000, 39, 2766–
3
(4H, m), 1.3 (6H, m); C NMR (CDCl /TMS): d 174.1
(2C), 51.4 (2C), 34.1 (2C), 29.0 (3C), 24.9 (2C); FT-IR
(Film) 1737 cm ; GC–MS (70 eV) m/z: 216 (0.5), 185
À1
2
771; (b) Santacesaria, E.; Ambrosio, M.; Sorrentino, A.;
Tesser, R.; Di Serio, M. Catal. Today 2003, 79–80, 59–65;
c) Oakley, M. A.; Woodward, S.; Coupland, K.; Parker,
D.; Temple-Heald, C. J. Mol. Catal. A: Chem. 1999, 150,
05–111; (d) Antonelli, E.; DÕAloisio, R.; Gambaro, M.;
Fiorani, T.; Venturello, C. J. Org. Chem. 1998, 63, 7190–
206.
(45), 152 (100), 124 (24), 111 (54), 83 (62), 74 (76), 55 (54).
22. Noyori, R.; Aoki, M.; Sato, K. Chem. Commun. 2003,
1977–1986.
(
1
23. For example, the oxidation of oleic acid in 10-fold larger
scale (oleic acid (2.28 g), NaIO
30 mL H O, 20 mL MeCN and 20 mL AcOEt with
4 3
(8.77 g), RuCl (50 mg) in
7
2
1
0. (a) Warwel, S.; Sojka, M.; Klass, M. R. gen. Top. Curr.
Chem. 1993, 164, 79–98; (b) Warwel, S; Klass, M. R. gen.
magnetic stirred, 2 h) gives after purification pure azelaic
acid in 75% yield (1.42 g).