Preparation of deuterium-labeled biotransformation products of 2,4,6-trinitrotoluene

Methods for the preparation of deuterium-labeled analogs to six prominent biotransformation products of the explosive 2,4,6-trinitrotoluene were developed. These are useful as reference standards for stable isotope dilution techniques and for solid state ²H NMR spectroscopic studies. Although syntheses for most of the target compounds in protiated form had been reported in the past, most of those were found to be poorly suited for the preparation of the deuterated materials. Selective reduction of [²H ₅]trinitrotoluene furnished [²H₅]-4,6-dinitro- 2-hydroxylaminotoluene, [²H₅]-2,6-dinitro-4- hydroxylaminotoluene, [²H₅]-2-amino-4,6-dinitrotoluene, and [²H₅]-4-amino-2,6-dinitrotoluene. The syntheses of [²H₁₀]-2,2′-azo-4,4′,6,6′- tetranitrotoluene and [²H₁₀]-4,4′-azo-2,2′,6, 6′-tetranitrotoluene were accomplished by selective oxidation of [ ²H₅]-2-amino-4,6-dinitrotoluene and [²H ₅]-4-amino-2,6-dinitrotoluene, respectively.