Oxidation of Sulfur and Amine Model Compounds.

Rapid removal of toxic agents from surfaces by techniques that employ atmospheric oxygen as the reactive species have considerable advantage over chemical or physical techniques that require spray, detergents, or surface coatings that are consumed in the reaction. This study is directed toward evaluating free radical oxidation and singlet oxygenation of sulfur and amine simulants for toxic agents at useful rates. The objectives of the work are to compare the rates of oxidation of some model sulfides and amines by free radicals and singlet oxygen to determine which reagents have the best potential as rapid and efficient decontaminating agents. To simplify the investigation the authors used two relatively nontoxic compounds, dibutyl sulfide Bu2S and ethyl diisopropylamine i-Pr2NEt as models for toxic agents containing sulfur and nitrogen. Photooxygenation of n-Bu2S with Rose Bengal RB and Methylene Blue MB gave rapid and high conversions of Bu2S to Bu2SO in MeOH with 0.0001 to 0.00001 M RB sensitizer turnover numbers for RB and MB were 10,000 and 35,000 respectively. Photooxygenation of iPr2NEt with RB or MB under conditions similar to those used for Bu2S gave less than 0.4 conversion of the amine. The free radical initiated oxidation of di-n-butyl sulfide Bu2S at 60C gives a slow conversion of sulfide to a complex mixture of products.