Milokhov D. Synthesis of functionalized azoles and azines based on 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitriles

The thesis is devoted to the investigation of the reactions of 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitriles with N- and C-nucleophiles in order to develop preparative methods for the synthesis of functionalized aza-heterocyclic compounds. It is shown that the initial attack of the nucleophilic reagent is directed primarily to the second position of the furanylidene fragment of the 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitriles, that was accomplished with ring opening of furan fragment. Further transformation depends on the nature of reagents and reaction conditions. The interaction of 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitriles with amino acids and dipeptides gave (Z)-2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles. The reaction of conformationally restricted and heterocyclic tertiary amines leads to the formation of betaines – 1-(2-hetaryl)-1-cyano-1-penten-2-olates. The ring transformation reaction of 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitrile with substituted acetonitrile as С-nucleophiles afforded fused cyanopyridine. The ring transformation reactions of 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitriles with amidines as 1,3-N,N-binucleophiles were investigated. Preparative synthesis of new of 6-amino-2-R-5-hetarylpyrimidine derivatives was developed. 2-Hetaryl-2-(1,3-dihydro-1-isobenzofuranylidene)acetonitriles were synthesized as benzo analogues of 2-hetaryl-2-(tetrahydro-2-furanyliden)acetonitrile.