Chemical Transformations of Trichothecenes. Nuclear Magnetic Resonance (NMR) Spectroscopic and Mass Spectrometric Characterization of Transformation Products of Verrucarol

摘要

Hypochlorite treatment of verrucarol, chosen as a prototype trichothecene similar to but simpler than T-2 toxin, resulted in quantitative conversion to a mixture of two chlorine-containing rearrangement products. Their structures were established by Carbon 13-Hydrogen 1 heteronuclear and 1H-1H homonuclear NMR chemical shift correlation experiments. Both products possess an unusual pentacyclic ring system which was resistant to further transformation at room temperature. At elevated temperatures in the presence of 1 N sodium hydroxide, however, fragmentation-rearrangement to two tricyclic C14 chloroketones and a chlorine-free C14 tetracyclic ketone took place. The structures of these products were similarly established.