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Relative esterifiability of the primary and secondary hydroxyl groups of glycerol
Author(s) -
Brandner J. D.,
Birkmeier R. L.
Publication year - 1960
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02672644
Subject(s) - primary (astronomy) , chemistry , intramolecular force , intermolecular force , equilibrium constant , glycerol , catalysis , reaction rate constant , elementary reaction , organic chemistry , molecule , kinetics , physics , quantum mechanics , astronomy
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 is ca. 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 from beta to alpha 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.