Synthesis of Non-Aromatic Pyrroles Based on the Reaction of Carbonyl Derivatives of Acetylene with 3,3-Diaminoacrylonitriles

• Published in: Molecules (Basel, Switzerland) Vol. 28; no. 8; p. 3576
• Main Authors: Silaichev, Pavel S, Dianova, Lidia N, Beryozkina, Tetyana V, Berseneva, Vera S, Maslivets, Andrey N, Bakulev, Vasiliy A
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 19.04.2023; MDPI
• Subjects: 1,2-dibenzoylacetylene; 3,3-diaminoacrylonitriles; 5-aminopyrroles; Acetylene; acetylenedicarboxylate (DMAD); Acrylonitriles; Carbon; Carbonyl compounds; Carbonyls; Chemical bonds; Chemical properties; Data analysis; Ions; pyrrol-3(2H)-ylidene acetates; Pyrroles; Substitutes; Germany; 1,2-dibenzoylacetylene; 5-aminopyrroles; acetylenedicarboxylate (DMAD); pyrrol-3(2H)-ylidene acetates; 3,3-diaminoacrylonitriles
• ISSN: 1420-3049; 1420-3049
• 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.