Kinetics and mechanism of the degradation of 1a-acetylmitomycin C in aqueous solution.

The acid-catalyzed degradation of mitomycin C is supposed to be governed, to a certain extent, by the protonation status of the aziridine nitrogen in the molecule as well as the protonation degree of the opened aziridine function in a key intermediate species, formed during mitomycin degradation. In order to obtain information about the contribution of the protonation degrees of these functions in controlling the degradation processes, we investigated the degradation of 1a-acetylmitomycin C in acidic aqueous solutions. In the presence of 0.001 mol/l phosphate buffers five 1-hydroxy and mono-acetyl mitosenes are formed, whereas in 1.0 mol/l acetate buffers a total of eight products could be identified, two of them being diacetyl mitosenes. Over the whole pH range studied the formation of 1,2-Z-mitosenes prevails, indicating that, contrary to mitomycin C, a pH-independent factor controls the ultimate 1,2-stereochemistry.