Oxidation of 17α-ethinylestradiol with Mn(III) and product identification

With increasing concern about the contamination of aquatic environments by estrogenic pollutants, removal of synthetic estrogens such as 17α-ethinylestradiol (EE2) has been widely studied, especially with respect to the treatment methods. However, the degradation products have rarely been identified. The purpose of this study was to identify structurally the oxidation products of EE2. Mn(III) was used as an oxidizing agent. To obtain sufficient oxidation products for HPLC, LC-MS and NMR spectroscopy, a highly concentrated solution of EE2 (1 mM) was prepared in a mixture of water and a water-miscible organic solvent. From HPLC of the reaction products, a single compound (I) was found to be predominant. From LC-MS, its molecular mass was found to be 294, and two hydrogens were believed to have been removed from EE2 (M.W. 296) to form a C{double bond, long}C double bond. The structure of compound I (position of the double bond) was determined using ¹H NMR, ¹³C NMR, H-H COSY, HSQC and HMBC. As minor products, isomeric dimers (M.W. 590) of EE2, as well as the products (M.W. 588) in which EE2 was coupled to compound I were also formed during the Mn(III)-mediated oxidation of EE2.