Photoextrusion of Molecular Nitrogen from Annulated 5-Alkylidene-4, 5-dihydro-1H-tetrazoles: Annulated Iminoaziridines and the First Triplet Diazatrimethylenemethane

摘要

Deprotonation of the annulated tetrazolium salts 4, 6, 8, 10, and 12 with sodium or potassium hydride yields the alkylidenedihydrotetrazoles 5, 7, 9, 11, and 13, respectively. While 5a and b are unstable, even in solution at low temperatures, 7, 9, 11, and 13 form yellow oils that are distilled under high vacuum. - Irradiation of solutions of 7, 9, and 11 in [D_8]toluene at -60℃ yields, besides molecular nitrogen, annulated iminoaziridines that have an exocyclic CN double bond, i.e. 14, 16, and 18, respectively. In addition, an equal amount of the isomer 19 with the endocyclic CN double bond is formed from 11. On thermolysis, 14, 16, and 18 undergo [2 + 1] cycloreversion into methyl isocyanide and the cyclic imines 15, 17, and 20, respectively. By contrast, 19 rearranges thermally to yield 18. While the doubly bridged alkylidenedihydrotetrazole 13a affords only unidentified decomposition products on photolysis, its methyl homologue 13b is converted into the hexahydronaphthyridine 22 which is also formed on thermolysis. -Irradiation of 13b in a 2-methyltetrahydrofuran or butyronitrile matrix at 77 K yields a triplet diradical showing a four-line EPR spectrum centred at 3362 G and a half-field transition (at 1669 G) with a hyperfine structure. The zero-field splitting parameters |D/hc| = 0.031 cm~(-1) and |Ehc| = 0.0014 cm~(-1) are obtained by simulation of the EPR spectrum. The signal-carrier is assigned the diazatrimethylenemethane structure 23 on the basis of the close similarity between its EPR spectrum and those of trimethylenemethane (28) and tris (N-methylimino)methane (29). - Structural features are discussed that are responsible for the observed differences between the photochemical pathways.