Chemistry of geminal diazides. Rearrangements to N-Cyano compounds

CHEMISTRY OF GEMINAL DIAZIDES. N-CYAN0 REARRANGEMENTS TO COMPOUNDS George Landen and Harold W. Moore Department of Chemistry, We have recently University of California, Irvine, shown that certain 2-azido-2-ene-1,4-diones contract to 2-cyano-1,3-diones (2-cyano-1,3-cyclopentenediones) California (azido-1,4-quinones) upon thermolysis, ring i.e., Also, we have observed that cyclic 2-azido-1,3-diones (2-azido-2-cyano-1,3-cyclo- .ti pentenediones) thermally ring expand to cyanoimines (cyanoazaquinones), 2. ,,2 R,=N,-+ 3 R,= CN. 2 In fact, the transformation, l+Ri= Ns -_‘2 R2 = Nt +2RJ /v plished directly upon thermolysis of certain 2,3-diazido-2-ene-1,4-diones qulnones) . 2 Thus, this vicinal traction vinyl diazide rearrangement followed by ring expansion with an overall in the ring system. Fromthese such as 2,2-diazido-l, g-diones, J R,= N, which are structurally N-cyanoimides, Therefore, results, j, version takes place. thermal chemistry interconversion by an initial ring con- of a nitrogen and carbon analogous to>and geminal diazides ring expand to azidoimines thus should subsequently the geminal diazide series should proceed (or tetrazoles)3 ring contract to by an initial ring where again an overall nitrogen and carbon intercon- To test this, the geminal diazides ,candzwere investigated. (2,3-diazido-1,4- one would anticipate that cyclic would thermally expansion followed by ring contraction proceeds = CN, can be accom- This study did demonstrate N prepared and their such a rearrangement.