Liquid-liquid extraction with dichloromethane is the Environmental Protection Agency's (EPA) method of choice for the analysis of acid or base neutral organic chemicals in water. Free radical chlorination and oxidation products of cyclohexene (the solvent preservative) in dichloromethane have been observed in extracts of chlorinated drinking water (after 10(5) fold concentration) by gas chromatography and gas chromatography-mass spectrometry. The chlorinated cyclohexene derivatives limit the quantitative and qualitative analysis of compounds eluting at Kovát's index less than 700-1000 and the use of these extracts for organoleptic and mutagenic studies. The effect of residual free chlorine in water on the cyclohexene present in the solvent was studied. Over ten cyclohexene derivatives were produced in every case when any residual free chlorine was present in the water. When chlorine is reduced to chloramine, the cyclohexene derivatives were greatly reduced in number and amount.