THE OXIDATION OF SULFUR-CONTAINING CYCLIC KETIMINES THE SULFOXIDE IS THE MAIN PRODUCT OF S-AMINOETHYL-CYSTEINE KETIMINE AUTOXIDATION

The products of autoxidation of S-aminoethyl-L-cysteine ketimine (AECK) have been analysed with the amino acid analyzer, with thin layer chromatography and with high performance liquid chromatography. Under the conditions of the assay (pH 8.5, 38-degrees-C, O2 bubbling) AECK is almost totally oxidized in 1.5 hours. Among the final products a component running fast in HPLC, named Cx1, has been isolated, reduced with NaBH4 and analysed. Reduced Cx1 resulted to show the same properties of synthetic thiomorpholine-3-carboxylic acid-S-oxide, known in the past literature with the name of ''chondrine''. On the basis of these results and by specific chromatographic tests, Cx1 has been identified as the sulfoxide of AECK. Among the other autoxidation products, thiomorpholine-3-one has been identified. The detection, after HCI hydrolysis, of glyoxylic acid and mesoxalic semialdehyde together with cysteamine indicates that compounds provided with easily cleavable S-C bonds, possibly thiohemiacetals or (and) thioesters, are the likely intermediates for other products. AECK sulfoxide and thiomorpholine-3-one are relatively stable and cannot be taken as the main intermediates for the remaining oxidation products.