Summary
A method has been devised for determining the relative esterifiability of the primary and secondary hydroxyl groups of glycerol. Contrary to the theory previously advanced by Feuge and Bailey, the primary and secondary hydroxyls are not equally esterifiable. The equilibrium constant favoring esterification of primary hydroxyl over secondary isca. 2.3 at reaction temperature (200°C.) and between 6 and 10 at room temperature. Since the equilibrium constant is substantially different at room temperature from that at reaction temperature, monoglycerides as customarily prepared are not at equilibrium at room temperature and undergo intramolecular migration of acyl groups frombeta toalpha hydroxyl positions. The rate of migration depends on the physical form of the ester and is accelerated by basic catalysts. In the vicinity of room temperature intermolecular rearrangement occurs only over very prolonged periods. The method of calculating relative esterifiability of primary and secondary hydroxyls should be applicable to other polyols.
Similar content being viewed by others
References
Birkmeier, R. L., and Brandner, J. D., J. Agr. Food Chem.,6, 471 (1958).
Brokaw, G. U., Perry E. S., and Lyman, W. C., J. Am. Oil Chemists’ Soc.,32, 194 (1955).
Crossley, A., Freeman, I. P., Hudson, B. J. F., and Pierce, J. H., J. Chem. Soc., 1959, 760.
Demarcq, M., La Revue Français des Corps Gras,5, 336 (1956).
Feuge, R. O., and Bailey, A. E., Oil and Soap,23, 259 (1946).
Martin, J. B., J. Am. Chem. Soc.,75, 5483 (1953).
Pohle, W. D., and Mehlenbacher, V. C., J. Am. Oil Chemists’ Soc.,27, 54 (1950).
Quinlan, P., and Weiser, H. J., J. Am. Oil Chemists’ Soc.,35, 325 (1958).
Smullin, C. F., and Olsanski, V. L., paper presented at annual meeting, American Oil Chemists’ Society, New Orleans, April 20–22, 1959.
Van Lohuizen, O. E., and Verkade, P. E., Rec. trav. chim.,79, 133 (1960).
West, E. S., Hoagland, C. L., and Curtis, G. H., J. Biol. Chem.,104, 627 (1934).
Author information
Authors and Affiliations
About this article
Cite this article
Brandner, J.D., Birkmeier, R.L. Relative esterifiability of the primary and secondary hydroxyl groups of glycerol. J Am Oil Chem Soc 37, 390–396 (1960). https://doi.org/10.1007/BF02672644
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02672644