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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 9, 1979 - Issue 7
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Original Articles

A Facile Method for Monoesterification of α, ω-Dicarboxylic Acids: Application to the Synthesis of Traumatic Acid, A Prostaglandin Synthon

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Pages 669-675 | Received 06 Apr 1979, Published online: 06 Dec 2006

References

  • Reuter , J. M. and Salomon , R. G. 1978 . J. Org. Chem. , 43 : 4247 and references therein
  • Rao , A. S. C. P. , Nayak , U. R. and Dev , S. 1975 . Synthesis , : 608 This paper also reports a synthesis of traumatic acid
  • Pacini , A. J. U. S. Patent . 3,542,826 . 1970 . See Chem. Abstr., 74, 53062f (1971)
  • English , J. Jr. , Bonner , J. and Haagen-Smit , A. J. 1939 . J. Am. Chem. Soc. , 61 : 3434
  • English , J. Jr. 1941 . J. Am. Chem. Soc. , 63 : 941
  • Mosettig , E. and Mozingo , R. 1948 . Org. Reactions , 4 : 362
  • Swann , S. Jr. , Oehler , R. and Buswell , R. J. 1943 . Organic Syntheses, Coll. , Vol. II , 276 New York, NY : John Wiley and Sons, Inc. . and references therein. Monoethyl sebacate has also been obtained by vapor phase pyrolysis (440°C) of diethyl sebacate. See W. J. Bailey and W. G. Carpenter, J. Org. Chem., 29, 1252 (1964)
  • No effort has been made yet to develop this particular reaction. The use of a less polar solvent mixture (e.g., hexane-cyclohexane) for extraction may result in a higher conversion of sebacic acid to the corresponding monoester
  • Sayles , D. C. and Degering , E. F. 1949 . J. Am. Chem. Soc. , 71 : 3161 Among the specific uses of such monoesters in organic synthesis are: They can be reduced to the corresponding ω-hydroxy acids, important precursors in the synthesis of lactones. For example, hydrogenation of monoethyl adipate in the presence of, copper chromite at 250°C and 135 atm. affords 6-hydroxyhexanoic acid (and the corresponding lactone) in excellent yield. See (b) Electrolysis of such monoesters has been utilized to prepare longer-chain α, ω-diesters:
  • Ito , Y. and Saegusam , T. 1977 . J. Org. Chem. , 42 : 2326 See S. Swann, Jr., and W. E. Garrison, Jr., “Organic Syntheses,” Coll. Vol. V, Wiley, New York, NY, 1973, p. 463
  • Acker , D. S. and Wayne , W. J. 1957 . J. Am. Chem. Soc. , 79 : 6483 Monoethyl adipate is a useful starting material in the total synthesis of dl-lipoic acid. See
  • Trost , B. M. , Salzmann , T. N. and Hiroi , K. 1976 . J. Am. Chem. Soc. , 98 : 4887 Certain monoesters have been utilized in total syntheses of insect pheromones. For specific examples, see and H. J. Bestmann, P. Range, and R. Kunstmann, Chem. Ber., 104, 65 (1971)
  • It is not necessary that the diacid be totally miscible with the aqueous ethanol layer. As the reaction proceeds, any residual solid material suspended in the aqueous mixture slowly dissolves
  • Moll , D. 1908 . Rec. trav. chim. , 26 : 373
  • Blaise , E. E. and Koehler , A. 1910 . Bull. soc. chim. , 7 : 215
  • Beilstein . Vol. 2 , 616 Part II
  • If one uses dilute aqueous sodium hydroxide to effect conversion of the monoester to the corresponding water-soluble salt, a substantial amount of hydrolysis of the monoester can occur while it is dissolved in the aqueous sodium hydroxide solution

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