Photochemistry of 1-Cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(piperazin-1-yl)quinoline-3-carboxylic Acid (=Ciprofloxacin) in Aqueous Solutions

The 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(piperazin-1-yl)quinoline-3-carboxylic acid (=ciprofloxacin; 1) undergoes low-efficiency (Φ=0.07) substitution of the 6-fluoro by an OH group on irradiation in H2O via the ππ* triplet (detected by flash photolysis, λmax 610 nm, τ 1.5 μs). Decarboxylation is a minor process (≤5%). The addition of sodium sulfite or phosphate changes the course of the reaction under neutral conditions. Reductive defluorination is the main process in the first case, while defluorination is accompanied by degradation of the piperazine moiety in the presence of phosphate. In both cases, the initial step is electron-transfer quenching of the triplet (kq=2.3⋅108M−1 s−1 and 2.2⋅107M−1 s−1, respectively). Oxoquinoline derivative 1 is much more photostable under acidic conditions, and in this case the F-atom is conserved, and the piperazine group is stepwise degraded (Φ=0.001).