Vulnerability of keto bile acids to alkaline hydrolysis.

Rigorous alkaline hydrolysis of the two primary (cholic and chenodeoxycholic) and of the two preponderant secondary (deoxycholic and lithocholic) bile acids found in bile led to excellent recoveries. Such was not the case with 11 different keto bile acid standards. Recoveries for a number of standards were unacceptably low and a variety of artefactural products were tentatively identified by gas-liquid chromatography. Keto bile acids bearing a keto gropu on C-3 were particularly vulnerable. In view of thee findings, quantitative and qualitative data reported on biological specimens submitted to saponification in ethanol, methanol, or even in water are of questionable significance.