Selective nitrosation of guanazine: Preparation of nitrosoguanazine and azidoaminotriazole

ORGN 139

Michael E. Sitzmann, sitzmannme@ih.navy.mil1, Magdy M. Bichay, bichaymm@ih.navy.mil2, John W. Fronabarger, jfronabarger@psemc.com3, Michael D. Williams, mwilliams@psemc.com3, William Sanborn Jr., bill.sanborn@psemc.com3, and Richard Gilardi, gilardi@nrl.navy.mil4. (1) Indian Head Division, Naval Surface Warfare Center, Indian Head, MD 20640, (2) Naval Sea Systems Command, Indian Head Division, Indian Head, MD 20640, (3) Pacific Scientific Energetic Materials Co, 7073 W. Willis Dr, Chandler, AZ 85226, (4) LSM 6030, Naval Research Laboratory
Reports of isolation of primary nitrosamines are rare, since these compounds readily convert to diazonium salts under normal reaction conditions. We report a method for selective nitrosation of guanazine (3,4,5-triamino-1,2,4-triazole), producing nitrosoguanazine (3-nitrosamino-4,5-diamino-1,2,4-triazole) (1) in 72% yield [nitrosation occurs on C-NH2 rather than on N-NH2 as shown by X-ray structure analyses on the K, Na salts (2a, 2b)]. Salts 2 have high stability (DSC: ca. 250 C) and are used to form salt complexes, e.g., treatment of 2a with aqueous Cu(NO3)2 gives a complex containing three Cu+2, three nitrosoguanazine anions and hydroxide (3), along with two nitrate counter-ions and two water molecules. Heating 1 in water produces high-purity 5-azido-3-amino-1,2,4-triazole.