Reversible Photohydration of Trenbolone Acetate Metabolites: Mechanistic Understanding of Product-to-Parent Reversion through Complementary Experimental and Theoretical Approaches

Environmental Science & Technology
Jonas BaltrusaitisDavid Cwiertny

Abstract

Photolysis experiments (in H2O and D2O) and quantum chemical calculations were performed to explore the pH-dependent, reversible photohydration of trenbolone acetate (TBA) metabolites. Photohydration of 17α-trenbolone (17α-TBOH) and 17β-trenbolone (17β-TBOH) occurred readily in simulated sunlight to yield hydrated products with incorporated H(+) at C4 and OH(-) at either C5 (5-OH-TBOH) or C12 (12-OH-TBOH) in the tetracyclic steroid backbone. Although unable to be elucidated analytically, theory suggests preferred orientations of cis-12-OH-TBOH (relative to C13 methyl) and trans-5-OH-TBOH, with the former most thermodynamically stable overall. Both experiment and theory indicate limited stability of trans-5-OH-TBOH at acidic pH where it undergoes concurrent, carbocation-mediated thermal rearrangement to cis-12-OH-TBOH and dehydration to regenerate its parent structure. Experiments revealed cis-12-OH-TBOH to be more stable at acidic pH, which is the only condition where its reversion to parent TBA metabolite occurred. At basic pH cis-12-OH-TBOH decayed quickly via hydroxide/water addition, behavior that theory attributes to the formation of a stable enolate resistant to dehydration but prone to thermal hydration. In a noteworthy ...Continue Reading

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Citations

Sep 7, 2019·Environmental Science. Processes & Impacts·Xingjian YangEdward P Kolodziej
May 24, 2019·Environmental Science & Technology·Andrew E KralDavid M Cwiertny
Apr 26, 2019·Organic Letters·Nicholas C PflugJames B Gloer
Oct 13, 2021·Environmental Science & Technology·Christopher J KnutsonJames B Gloer
Oct 30, 2021·Environmental Science & Technology·Jannis WenkSilvio Canonica

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