Metalated Azolo[1,2,4]triazines. I. Synthesis of 2-(6-tert-Butyl-5-oxo-4,5-dihydro-1,2,4-triazin-3(2H)-ylidene)acetonitriles via Ring Opening Degradation of 3-tert-Butyl-7-lithio-4-oxo-4H-pyrazolo[5,1-c][1,2,4]triazin-1-ides

1,7,8-Polymetalated 3-tert-butyl-8-R-4-oxo-4H-pyrazolo[5,1-c][1,2,4]triazines (M = Li, Na; R = CO2Et, CN, H, D, and Li) have been generated for the first time using acidic NH deprotonation and lithium/bromine exchange method at -112 divided by -97 degrees C. The rapid pyrazole ring opening degradation of the unstable 7-lithio-4-oxopyrazolo[5,1-c][1,2,4] triazines at -97 degrees C led to formation of 2-(6-tert-butyl-5-oxo-4,5-dihydro-1,2,4-triazin-3(2H)-ylidene)acetonitriles. Furthermore, lithium, sodium ((6-tert-butyl-5-oxo-5H-1,2,4-triazin-2,4-diid-3-ylidene)(cyano) methyl) lithium was successfully generated from 7,8-dibromo-3-tert-butylpyrazolo[5,1-c][1,2,4] triazin-4(6H)-one, sodium hydride, and tert-butyl lithium, and an electrophile trapping using H2O, dimethylformamide, t-BuCOCl, and PhCOCl allowed the selective side-chain functionalization. Structures of the isolated products have been established on the basis of IR, H-1, H-2, C-13 NMR, and high-resolution mass spectra.