604
Vol. 51, No. 5
306.0475.
3) Some monographs for the chemistry of carboxylic acids and their de-
rivatives, see: Patai S., “The Chemistry of Acid Derivatives,” Part 1
and 2, John Wiley and Sons, Chichester, 1979.
4) Some monographs for the chemistry of carboxylic acids and their de-
rivatives, see: Sutherland I. O. (ed.), “Comprehensive Organic Chem-
istry,” Vol. 2, Part 9, Pergamon Press, Oxford, 1979.
4c: Colorless oil; IR (neat) 1716 (CO), 1462, 1444, 1087, 1057 (SO), 747,
688 cmϪ1. 1H-NMR d 0.84—0.90 (6H, m), 1.14—1.35 (2H, m), 1.85—1.97
(1H, m), 2.22—2.79 (2H, m), 4.95, 4.96, 4.97, 4.99 (each 0.25H, s), 7.54—
7.72 (5H, m). MS m/z (%) 272 (Mϩ, 10), 157 (7), 125 (100), 99 (34). Calcd
for C13H17ClO2S: M, 272.0637. Found: m/z 272.0645.
4d: Colorless oil; IR (neat) 1732, 1716 (CO), 1444, 1089, 1056 (SO),
5) Some monographs for the chemistry of carboxylic acids and their de-
rivatives, see: Patai S., “The Chemistry of Acid Derivatives,” Part 1
and 2, John Wiley and Sons, Chichester, 1992.
6) Some recent methods for the oxidation of primary alcohols and alde-
hydes to carboxylic acids and their derivatives, see: McDonald C. E.,
Nice L. E., Shaw A. W., Nestor N. B., Tetrahedron Lett., 34, 2741—
2744 (1993).
747, 688 cmϪ1 1H-NMR d 0.89 (3H, t, Jϭ7.0 Hz), 1.29—1.33 (4H, m),
.
1.44—1.47 (2H, m), 2.08—2.12 (2H, m), 2.37—2.40 (2H, m), 2.54—2.62
(0.5H, m), 2.71—2.80 (0.5H, m), 2.92—3.03 (1H, m), 5.06 (0.45H, s), 5.07
(0.55H, s), 7.54—7.70 (5H, m). MS m/z (%) 324 (Mϩ, 0.4), 307 (19), 151
(7), 143 (8), 125 (100). Calcd for C17H21ClO2S: M, 324.0950. Found: m/z
324.0965.
Undecanoic Acid (5a) To a flame-dried flask KH (24 mg; 0.6 mmol)
and 2 ml of THF were added. To this suspension was added dropwise a solu-
tion of 4a (100 mg; 0.3 mmol) in 1 ml of THF and the reaction mixture was
stirred at 0 °C for 30 min. After the evolution of H2 ceased, the reaction mix-
ture was cooled to Ϫ78 °C and t-BuLi (1.2 mmol) was added and the reac-
tion mixture was stirred for 20 min. The reaction was quenched by adding
5% NaOH (0.5 ml) and the reaction mixture was stirred for 10 min, and at
0 °C for 10 min. To the reaction mixture was added CHCl3 and the whole
was extracted three times with 5 ml of 5% NaOH. The water layers were
combined and acidified with HCl and extracted with CHCl3. The product
was purified with short silica-gel column to give 44 mg (78%) of 5a as a col-
orless oil. 5a and 5b are known compounds.
7) Some recent methods for the oxidation of primary alcohols and alde-
hydes to carboxylic acids and their derivatives, see: Rhee H., Kim J.
Y., Tetrahedron Lett., 39, 1365—1368 (1998).
8) Some recent methods for the oxidation of primary alcohols and alde-
hydes to carboxylic acids and their derivatives, see: Zhao M., Song J.
L. Z., Desmond R., Tschaen D. M., Grabowski E. J. J., Reider P. J.,
Tetrahedron Lett., 39, 5323—5326 (1998).
9) Some recent methods for the oxidation of primary alcohols and alde-
hydes to carboxylic acids and their derivatives, see: Zhao M., Mano J.
L. E., Song Z., Tschaen D. M., Grabowski E. J. J., Reider P. J., J. Org.
Chem., 64, 2564—2566 (1999).
10) Hase T. A., “Umpoled Synthons,” John Wiley and Sons, New York,
1987.
5c: Colorless oil; IR (neat) 2961, 2875, 1712 (CO), 1463, 1102 cmϪ1. 1H-
NMR d 0.86—0.89 (6H, m), 1.15—1.51 (4H, m), 1.65—1.72 (1H, m),
2.27—2.42 (2H, m), 10.07 (1H, s). MS m/z (%) 113 (7), 57 (100), 41 (38).
11) Nakamura E., Kuwajima I., J. Am. Chem. Soc., 99, 7360—7362
(1977), and the references cited therein.
5d: Colorless oil; IR (neat) 2932, 2859, 1712 (CO), 1435, 1243 cmϪ1. 1H- 12) Ehlinger E., Magnus P., J. Am. Chem. Soc., 102, 5004—5011 (1980),
NMR d 0.89 (3H, t, Jϭ7.1 Hz), 1.20—1.56 (6H, m), 1.81 (2H, quintet,
Jϭ7.1 Hz), 2.11—2.15 (2H, m), 2.22—2.25 (2H, m), 2.49 (2H, t, Jϭ7.4
Hz), 9.79 (1H, bs). MS m/z (%) 181 (8), 154 (17), 126 (67), 81 (100).
and the references cited therein.
13) Nakamura E., Kuwajima I., J. Am. Chem. Soc., 105, 651—652 (1983),
and the references cited therein.
14) Werstiuk N. H., Tetrahedron, 39, 205—268 (1983), and the references
cited therein.
Acknowledgments This work was supported by a Grant-in-Aid for Sci-
entific Research No. 11640545 from the Ministry of Education, Culture, 15) Pastor I. M., Yus M., Tetrahedron Lett., 41, 5335—5339 (2000), and
Sports, Science and Technology, Japan, which is gratefully acknowledged.
We thank Mr. Akira Nakamura for his technical assistance.
the references cited therein.
16) Satoh T., Unno H., Mizu Y., Hayashi Y., Tetrahedron, 53, 7843—7854
(1997).
References and Notes
1) Some monographs for the chemistry of carboxylic acids and their de-
17) Satoh T., Nakamura A., Iriuchijima A., Hayashi Y., Kubota K., Tetra-
hedron, 57, 9689—9696 (2001).
rivatives, see: Patai S., “The Chemistry of Carboxylic Acids and Es- 18) Grieco P. A., Pogonowski C. S., J. Org. Chem., 39, 732—734 (1974).
ters,” John Wiley and Sons, London, 1969. 19) Kuwajima I., Iwasawa H., Tetrahedron Lett., 1974, 107—110 (1974).
2) Some monographs for the chemistry of carboxylic acids and their de- 20) Solladie G., Colobert F., Denni D., Tetrahedron: Asymmetry, 9, 3081—
rivatives, see: Zabicky J., “The Chemistry of Amides,” John Wiley and
Sons, London, 1970.
3094 (1998).
21) Tsuchihashi G., Ogura K., Bull. Chem. Soc. Jpn., 44, 1726 (1971).