Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia.
Department of Chemistry, Perm State University, 15 Bukireva Street, Perm 614990, Russia.
Molecules. 2023 Apr 19;28(8):3576. doi: 10.3390/molecules28083576.
The reaction of 3,3-diaminoacrylonitriles with DMAD and 1,2-dibenzoylacetylene was studied. It is shown that the direction of the reaction depends on the structure both of acetylene and of diaminoacrylonitrile. In the reaction of DMAD with acrylonitriles bearing a monosubstituted amidine group, 1-substituted 5-amino-2-oxo-pyrrole-3(2)ylidenes are formed. On the other hand, a similar reaction of acrylonitriles containing the ,-dialkylamidine group affords 1--5-aminopyrroles. In both cases, pyrroles containing two exocyclic double bonds are formed in high yields. A radically different type of pyrroles containing one exocyclic C=C bond and sp hybrid carbon in the cycle is formed in reactions of 3,3-diaminoacrylonitriles with 1,2-diaroylacetylenes. As in reactions with DMAD, the interaction of 3,3-diaminoacrylonitriles with 1,2-dibenzoylacetylene can lead, depending on the structure of the amidine fragment, both to - and 1-substituted pyrroles. The formation of the obtained pyrrole derivatives is explained by the proposed mechanisms of the studied reactions.
研究了 3,3-二氨基丙烯腈与 DMAD 和 1,2-二苯甲酰基乙炔的反应。结果表明，反应的方向取决于乙炔和二氨基丙烯腈的结构。在 DMAD 与带有单取代脒基的丙烯腈的反应中，形成了 1-取代的 5-氨基-2-氧代-吡咯-3(2)亚基。另一方面，类似的含有,-二烷基脒基的丙烯腈的反应得到了 1--5-氨基吡咯。在这两种情况下，都以高产率形成了含有两个外环双键的吡咯。在 3,3-二氨基丙烯腈与 1,2-二芳基乙炔的反应中，形成了一种 radically 不同类型的吡咯，其含有一个外环 C=C 键和环中的 sp 杂化碳。与 DMAD 的反应一样，3,3-二氨基丙烯腈与 1,2-二苯甲酰基乙炔的相互作用可以根据脒基片段的结构，同时导致 -和 1-取代的吡咯的形成。所得到的吡咯衍生物的形成通过所研究反应的提出的机制来解释。
