Synthesis of 14C-Labelled Octahydor-1,3, 5,7-Tetranitro-1,3,5,7- Tetrazocine HMx0 and 15N-Isotopic Hexahyrro-1,3,5- Trinitro-1,3,5-Triazine (RDX) for use in Microcosm Experiments

摘要

Within the framework of an R & D project on bioremediation of soils contaminated with energetic compounds, the biodegradation of energetic nitramine products such as octogen (HMX) and hexogen (RDX) is under study. Microcosm assays can be performed with radioactive carbon-14 labelled substrates or with isotopic nitrogen-15 labelled substrates in order to ascertain and monitor their biodegradation pathways and to optimize parameters for a bioremediation process. To synthesize C(14)HMX, acetylation of labelled hexamethylenetetramine (C(14) HMTA) was done yielding 3,7-diacetyl-1,3,5, 7-tetraazabicyclo-(3.3.10- nonane(C(14)DAPT) which was nitrated to obtain 1,5-diacetyloctahydro-3,7-dintro- a,3,5,7-tetrazocine (C(14)DADN) in one step. Nitrolysis of C(14)DADN was achieved using a mixture of 100% nitric acid and phosphorus pentoxide to yield C(14)HMX. The synthesis of this carbon-14 labelled HMX was optimized first using cold starting materials and then conducted with labelled compounds. To synthesize N(15)RDX, nitration of nitrogen-15 hexamethylenetetramine (N(15)HMTA) was done according to the Hale Process. N(15)HMTA was prepared by reaching cold formaldehyde with isotopic nitrogen-15 ammonium hydroxide.