Harold Wilson

The Reaction of 2,4,6-Trinitrotoluene and 2,4,6-Trinitrotoluene-d3 with Sodium Isopropoxide in Isopropyl Alcohol

The reaction of sodium isopropoxide with 2,4,6-trinitrotoluene (TNT) and TNT-d3 (deuterated methyl group) in isopropanol has been investigated using stopped-flow techniques. Two absorbing species, identified as a σ-complex and the TNT anion (TNT−) are formed in this reaction. The formation of TNT− involves a rate determining proton transfer as shown by the observation of an isotope effect A spectrum of the σ-complex was calculated from initial rate data and was observed experimentally at low temperatures (λmax = 435, 495 nm). The effects of added salts on rates and equilibria of σ-complex and TNT− formation have been determined.In this study the possible involvement of free alkoxide ions and ion-pairs in the reactions has been evaluated. The free alkoxide ion is the more reactive species in deuteron transfer whilst in σ-complex formation the free ions and ion-pairs have comparable reactivity. A rationale of this behavior is presented.The kinetic parameters are, for deuteron transfer: kiD = 850 ± 100 M−1s−...