3-Pyridazinylnitrenes and 2-Pyrimidinylnitrenes

Abstract

Mild flash vacuum thermolysis of tetrazolo[1,5-b]pyridazines 8T generates small amounts of 3-azidopyridazines 8A (8aA, IR 2145, 2118 cm(-1); 8bA, 2142 cm(-1)). Photolysis of the tetrazoles/azides 8T/8A in Ar matrix generates 3-pyridazinylnitrenes 9, detected by ESR spectroscopy (9a: D/hc = 1.006; E/hc = 0.003 cm(-1)). Cyanovinylcarbenes 11, derived from 4-diazobut-2-enenitriles 10, are also detected by ESR spectroscopy (11a: D/hc = 0.362; E/hc = 0.021 cm(-1)). Carbenes 11 rearrange to cyanoallenes 12 and 3-cyanocyclopropenes 13. Triazacycloheptatetraenes 20 were not observed in the photolyses of 8. Photolysis of tetrazolo[1,5-a]pyrimidines/2-azidopyridmidines 18T/18A in Ar matrices at 254 nm yields 2-pyrimidinylnitrenes 19, observable by ESR, UV, and IR spectroscopy (19a: ESR: D/hc = 1.217; E/hc = 0.0052 cm(-1)). Excellent agreement with the calculated IR spectrum identifies the 1,2,4-triazacyclohepta-1,2,4,6-tetraenes 20 (20a, 1969 cm(-1); 20b, 1979 cm(-1)). Compounds 20 undergo photochemical ring-opening to 1-isocyano-3-diazopropenes 23. Further irradiation also causes Type II ring-opening of pyrimidinylnitrenes 19 to 2-(cyanimino)vinylnitrenes 21 (21a: D/hc = 0.875; E/hc = 0.00 cm(-1)), isomerization to cyaniminoketenimine 25 (2044 cm(-1)), and cyclization to 1-cyanopyrazoles 22. The reaction mechanisms are discussed and supported by DFT calculations on key intermediates and pathways. There is no evidence for the interconversion of 3-pyridazinylnitrenes 9 and 2-pyrimidinylnitrenes 19.