Synthesis of Non-Aromatic Pyrroles Based on the Reaction of Carbonyl Derivatives of Acetylene with 3,3-Diaminoacrylonitriles
Pavel S. Silaichev,
Lidia N. Dianova,
Tetyana V. Beryozkina,
Vera S. Berseneva,
Andrey N. Maslivets,
Vasiliy A. Bakulev
Affiliations
Pavel S. Silaichev
Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia
Lidia N. Dianova
Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia
Tetyana V. Beryozkina
Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia
Vera S. Berseneva
Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia
Andrey N. Maslivets
Department of Chemistry, Perm State University, 15 Bukireva Street, Perm 614990, Russia
Vasiliy A. Bakulev
Technology of Organic Synthesis Department, Ural Federal University Named after the First President of Russia B. N. Yeltsin, 19 Mira Street, Yekaterinburg 620002, Russia
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(2H)ylidenes are formed. On the other hand, a similar reaction of acrylonitriles containing the N,N-dialkylamidine group affords 1-NH-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 sp3 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 NH- and 1-substituted pyrroles. The formation of the obtained pyrrole derivatives is explained by the proposed mechanisms of the studied reactions.
