434338-63-3Relevant academic research and scientific papers
New products from the heptalene-forming reaction of azulenes and acetylenedicarboxylates in polar media
Singh, Gurmit,Linden, Anthony,Abou-Hadeed, Khaled,Hansen, Hans-Juergen
, p. 27 - 59 (2007/10/03)
A number of azulenes 1, in particular those with π-substituents at C(6) such as phenyl, 3,5-dimethylphenyl, and 4-biphenyl, have been reacted with 3 mol-equiv. of dimethyl acetylenedicarboxylate (ADM) in MeCN at 110° (cf. Scheme 1). Main products had been, in all cases, the corresponding heptalene-4,5-dicarboxylates 2. However, a whole number of side products, mainly rearranged (1 + 2)-adducts with two molecules of ADM, in amounts of 0.2-9% were also isolated and characterized (cf. Scheme 2). The 2a,8a-dihydro-3,4-ethenoazulene-1,2-dicarboxylates 14, formed by energetically favorable ring closure from the solvent-stabilized zwitterions 15, resulting from bond heterolysis in the primary cycloadducts 12 (cf. Scheme 3), have been mechanistically identified as the pivotal intermediates responsible for the formation of all side product (cf. Schemes 5, 9, 12, and 13). Deuterium-labeling experiments were in agreement with the proposed mechanisms, indicating that sigmatropic [1,5s]-H shifts in 14 (cf. Scheme 6) as well as isoconjugate [1,4s]-H shifts in resonance-stabilized zwitterions of type 21 (cf. Scheme 9) are the crucial steps for side-product formation. It is postulated that a concluding antarafacial 8e-dyotropic rearrangement is responsible for the appearance of the 2,4a-dihydrophenanthrene-tetracarboxylates of type trans-6 (cf. Scheme 9) in the reaction mixtures, which further rearrange thermally by a not fully understood mechanism into the isomeric tetracarboxylates 7 (cf. Schemes 10 and 11). Most surprising is the presence of a small amount (0.3-1%) of the azulene-4,5,7,8-tetracarboxylate 9 in the reaction mixture of azulene 1a and ADM. It is proposed that the formation of 9 is the result of a [1,5s]-C shift in the spiro-linked intermediates 24, which, after prototropic shift and take-up of a third molecule of ADM, disintegrate by a retro-Diels-Alder reaction into 9 and the phthalic diesters 30 (cf. Scheme 12). The UV/VIS spectra of the π-substituted heptalene-4,5-dicarboxylates 2d-2f and their double-bond shifted (DBS) forms 2d-2f (cf. Table 4 and Figs. 9-12) exhibit in comparison with the heptalene-dicarboxylates 2a and 2′a, carrying a t-Bu group at C(8), only marginal differences, which are mainly found in the relative intensity and position of heptalene bands II and III.
