Treatment of 3-tert-butyl-8-R-pyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]triazine-4,10(6H,9H)-diones with diphosphorus pentasulfide gave 3-tert-butyl-8-R-pyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]triazine-4,10(6H,9H)-dithiones whose hydrazinolysis afforded 3-tert-butyl-10-hydrazinyl-8-R-pyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]triazine-4(6H)-thiones. 3-tert-Butyl-10-hydrazinylpyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]-triazine-4(6H)-thione reacted with sodium nitrite in phosphoric or polyphosphoric acid yielding 10-azido-3-tert-butylpyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]triazine-4(6H)-thione and 3-tert-butyltetrazolo[1″,5″:3′,4′]pyrimido[5′,6′:3,4]pyrazolo[5,1-c][1,2,4]triazin-4(12H)-one, respectively.