Zum verhalten konjugierter diene gegenüber C6H5J(OAc)2-(CH3)3SiN3

IR-spectroscopic measurements between ?60° and 0°C show the existence of C₆H₅J(OAc)_2-n(N₃)_n generated by the reaction of C₆H₅J(OAc)₂ with (CH₃)₃SiN₃. C₆H₅J(OAc)_2-n(N₃)_n reacts with 2,3-dimethylbutad to give substances C₁₂H₂₀N₆ (1), having the probable structure of 2,3,5-trimethyl-3,6-di-azidomethyl-heptadiene-1,5 and 3,4-diazido-3-methylbutanone-2 (2). Likewise we get from 1,3-cyclohexadiene the diazide C₁₂H₁₆N₆ (3), and 4-azido-cyclohexene-2-on-1 (4). Analogously from cyclopentadiene we get the carbonylcompound 4-azido-cyclopentene-2-on-1 (5). E-5-azido-hexene-3-on (8) results from 2,4-E,Z-hexadiene. 1,3-cyclooctadiene gives as main product 6 (4-azido-cyclooctene-2-on-1) but also some 7 (8-azido-cyclooctene-2-on-1) emerging from an attack on positions 1 and 2.Δ^1,3, Δ^3,5 and Δ^4,6-cholestadiene yield in a regio- and stereo-specific manner the products 9 (1α-azidocholestene-2-on-4), 10 (6β-azidocholestene-4-on-3) and 11 (4β-azidocholestene-5-on-7). These last examples confirm our suggestions from the preponderance of the 1,4-functionalisation.