Journal of the American Oil Chemists Society

, Volume 38, Issue 11, pp 600–605 | Cite as

Low temperature aminolysis of methyl stearate catalyzed by sodium methoxide

  • Edmund F. JordanJr.
  • William S. Port
Technical

Abstract

Aminolysis of methyl stearate by both primary and secondary amine catalyzed by sodium methoxide was found to be rapid at 30°C. under anhydrous conditions. With primary amines under optimum conditions (mole ratio to ester: amine, 10; catalyst, 0.12), the minimum reaction times necessary to obtain yields of amide over 90% were:n-butylamine, 30 min.;iso-butyl-, 1 hour; allyl-, 1.8 hr.; benzyl-, 3.2 hr.;sec-butyl-, 16 hr.; ammonia (a heterogenous reaction requiring an optimum triethylamine to ester ratio of 2 ml./g. and a catalyst mole ratio of 0.20) 2 days. Secondary amines reacted rapidly at 30°C. (15 min. to 24 hr. for a 90% yield of amide) when the nitrogen atom was joined into a saturated ring or held at least one methyl group, but very slowly even at 100°C, when the substituent was dialkyl larger than methyl. Uncatalyzed, all reactions were extremely slow.

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References

  1. 1.
    Grunwald, F.A. (Mead Johnson & Co.), U.S. 2,764,613 (1956).Google Scholar
  2. 2.
    Katzman, M.B., and Epstein, A.K. (Emulsol Corporation), U.S. 2,173,448 (1939).Google Scholar
  3. 3.
    Meade, E.M. (Lankro Chemicals Ltd.), U.S. 2.464,094 (1949).Google Scholar
  4. 4.
    Naudet, M., Sambuc, E., Desnuelle, P., and Reutenauer, G., Bull. Soc. Chim., France, 476–480 (1952).Google Scholar
  5. 5.
    Ricciardi, L.G., and Digeronimo, J.P. (Colgate-Palmolive Co.), U.S. 2,843,612 (1958).Google Scholar
  6. 6.
    Russell, P.B., J. Am. Chem. Soc.,72, 1853–1854 (1950).CrossRefGoogle Scholar
  7. 7.
    Shapiro, S.L., Rose, I.M., and Freedman, L., J. Am. Chem. Soc.,80, 6065–6071 (1958).CrossRefGoogle Scholar
  8. 8.
    Tesoro, G.C. (Onyx Oil and Chemical Co.)U.S. 2,844,609 (1958).Google Scholar
  9. 9.
    Baltzly, R., Berger, I.M., and Rothstein, A.A., J. Am. Chem. Soc.,72, 4149–4152 (1950).CrossRefGoogle Scholar
  10. 10.
    Betts, R.L., and Hammett, L.P., J. Am. Chem. Soc.,59, 1568–1572 (1937).CrossRefGoogle Scholar
  11. 11.
    Bunnett, J.F., and Davis, G.T., J. Am. Chem. Soc.,82, 665–674 (1960).CrossRefGoogle Scholar
  12. 12.
    Watanabe, W.H., and De Fonso, L.R., J. Am. Chem. Soc.,78, 4542–4549 (1956).CrossRefGoogle Scholar
  13. 13.
    Baldy, J., Naudet, M., and Desnuelle, P., Bull. Soc. Chim., France, 1172–1176 (1954).Google Scholar
  14. 14.
    Gorvin, J.H., J. Chem. Soc., 732–735 (1945).Google Scholar
  15. 15.
    Kleinberg, J., and Audrieth, L.F., Organic Syntheses, Collective Vol. 3, 516–518 (1955).Google Scholar
  16. 16.
    Naudet, M., Baldy, J., and Desnuelle, P. Bull. Soc. Chim., France, 1167–1172 (1954).Google Scholar
  17. 17.
    Paden, J.H., and Adkins, H., J. Am. Chem. Soc.,58, 2487–2499 (1936).CrossRefGoogle Scholar
  18. 18.
    Roe, E.T., Scanlan, J.T., and Swern, D., J. Am. Chem. Soc.,71, 2215–2218 (1949).CrossRefGoogle Scholar
  19. 19.
    Roe, E.T., Stutzman, J.M., Scanlan, J.T., and Swern, D., J. Am. Oil Chemists’ Soc.,29, 18–22 (1952).CrossRefGoogle Scholar
  20. 20.
    Wojcik, B., and Adkins, H., J. Am. Chem. Soc.,56, 2419–2424 (1934).CrossRefGoogle Scholar
  21. 21.
    Washburne, R.N., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,80, 5963–5965 (1958) and preceding papers.CrossRefGoogle Scholar
  22. 22.
    Arnett, E. McC., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,72, 5635–5638 (1950).CrossRefGoogle Scholar
  23. 23.
    Morrell, G.F., J. Chem. Soc., 2698–2707 (1914).Google Scholar
  24. 24.
    French, H.E., and Wrightsman, G.G., J. Am. Chem. Soc.,60, 50–51 (1938).CrossRefGoogle Scholar
  25. 25.
    Gordon, M., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,70, 1946–1953 (1948).CrossRefGoogle Scholar
  26. 26.
    Swern, D., and Jordan, E.F. Jr., J. Am. Chem. Soc.,70, 2334–2339 (1948).CrossRefGoogle Scholar
  27. 27.
    Gordon, M., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,71, 1245–1250 (1949).CrossRefGoogle Scholar
  28. 28.
    Arnett, E. McC., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,73, 5393–5395 (1951).CrossRefGoogle Scholar
  29. 29.
    Jung, S.L., Miller, J.G., and Day, A.R., J. Am. Chem. Soc.,75, 4664–4665 (1953).CrossRefGoogle Scholar
  30. 30.
    Ratchford, W.P., and Fisher, C.H., J. Am. Chem. Soc.,69, 1911–1914 (1947).CrossRefGoogle Scholar
  31. 31.
    Ratchford, W.P., Lengel, J.H., and Fisher, C.H., J. Am. Chem. Soc.,71, 647–651 (1949).CrossRefGoogle Scholar
  32. 32.
    Ratchford, W.P., and Fisher, C.H., J. Org. Chem.,15, 317–325 (1950).CrossRefGoogle Scholar
  33. 33.
    Magne, F.C., Dupuy, H.P., and Goldblatt, L.A., J. Am. Oil Chemists’ Soc.,36, 635–637 (1959) and preceding papers.CrossRefGoogle Scholar
  34. 34.
    Walpole, A.L., Roberts, D.C., Rose, F.L., Hendry, J.A., and Homer, R.F., Brit. J. Pharmacal,9, 306 (1954).Google Scholar
  35. 35.
    Bunnett, J.F., Robison, M.M., and Pennington, F.C., J. Am. Chem. Soc.,72, 2378–2381 (1950).CrossRefGoogle Scholar
  36. 36.
    Magnani, A., and McElvain, S.M., J. Am. Chem. Soc.,60, 813–820 (1938).CrossRefGoogle Scholar
  37. 37.
    Adickes, F., v. Müddenhein, S., and Simson, W., Ber.66, 1904–1909 (1933).Google Scholar

Copyright information

© The American Oil Chemists’ Society 1961

Authors and Affiliations

  • Edmund F. JordanJr.
    • 1
  • William S. Port
    • 1
  1. 1.Eastern Regional Research LaboratoryPhiladelphia 18

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