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Kinetic evaluation of 3β-hydroxycholest-5-en-7-one (7-ketocholesterol) stability during saponification

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Journal of the American Oil Chemists' Society

Abstract

To clarify conflicting information regarding 7-ketocholesterol (7-KC) recovery from saponification, we evaluated the stability of 7-KC in methanolic alkaline medium. We added 1 N alcoholic KOH to 7-KC or lard spiked with 7-KC and held the mixtures at 45, 55, 65, and 75°C for different times to simulate various saponification conditions. Gas-chromatographic determination of residual 7-KC with 5α-cholestane as the internal standard (IS) showed that the higher the saponification temperature, the greater the 7-KC degradation. Hot saponification at 75°C for 30 min caused extensive destruction and left only 31% 7-KC. 7-KC loss during saponification could be described by pseudo first-order kinetics, and the dependence of degradation rate on temperature (T, K) byk (h−1)=(2.6×1017) exp (−1.36×104/T). As predicted by the kinetic equation, 7-KC loss during room-temperature saponification (21°C) was practically negligible; following the exposure of 7-KC or lard spiked with 7-KC to 1 N alcoholic KOH for 18 h, about 97% 7-KC was recovered. 6-Ketocholestanol, when used as an IS, should be looked at carefully because of potential tautomerization, leading to the formation of two enol isomers when in extended contact with trimethylsilyl derivatization reagents.

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Authors and Affiliations

  1. Crown Laboratories, Inc., 89119, Las Vegas, Nevada

    Peter W. Park

  2. Department of Food Science and Nutrition, University of Minnesota, 55108, St. Paul, Minnesota

    Francesc Guardiola & Paul B. Addis

  3. Nutrition and Food Science Unit, Faculty of Pharmacy, University of Barcelona, Barcelona, Spain

    Francesc Guardiola

  4. Analtek, 47711, Evansville, Indiana

    Susan H. Park

Authors
  1. Peter W. Park
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  2. Francesc Guardiola
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  3. Susan H. Park
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  4. Paul B. Addis
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Park, P.W., Guardiola, F., Park, S.H. et al. Kinetic evaluation of 3β-hydroxycholest-5-en-7-one (7-ketocholesterol) stability during saponification. J Amer Oil Chem Soc 73, 623–629 (1996). https://doi.org/10.1007/BF02518118

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  • DOI: https://doi.org/10.1007/BF02518118

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