Further Studies of the Interaction of Carbonyl Compounds with Organometallic Azides, the Novel Reaction of Benzoquinone with Trimethylsilyl Azide, Homestead Archives
Unlike the reaction of trimethylsilylazide (TMSA), (1), with maleic anhydride, which results in nitrogen ring insertion and production of “oxauracil” in high yield1, reaction of TMSA with benzoquinone in warm non polar solvents gave a complex mixture of products, primarily 2,5-diazido benzoquinone, (2), 1,4-BIS-(trimethylsiloxy)benzene, (3), “quinhydrone”, (4), the 1:1 adduct of hydroquinone, and hydroquinone (6). The results were postulated to involve rapid conjugate addition of 2 moles of TMSA to benzoquinone, yielding reactive intermediate bis-1,4-trimethylsiloxy, 3,6-diazido, 1,4-cyclohexadiene, (5). A rapid oxidation-reduction reaction of 5 with quinone yields hydroquinone (6) and bis-1,4-trimethylsiloxy-2,5-diazidobenzene (7). 6 further reacts in a similar fashion with benzoquinone yielding 4, while 7 further reacts with benzoquinone yielding 2 and 3. The reaction has limited synthetic utility due to the number of complex oxidation-reduction pathways available in this system.