Intramolecular Transformations of 3-Cyanoamino- and 3-Cyanoimino-1,2-diferrocenylcyclopropenes

Abstract

3-Cyanoamino-1,2- and -2,3-diferrocenylcyclopropenes 6a,b and 11a,b prepared by the reaction of diferrocenylcyclopropenylium salts with sodium cyanamide undergo smooth intramolecular transformations with both conservation of the three-membered ring [affording 3-cyanoimino-1,2-diferrocenylcyclopropene (8)] and its opening [affording Z-3-morpholino- and Z-3-piperidino-3-(cyanoimino)-1,2-diferrocenylprop-1-enes 7a,b and Z-3-cyanoimino-2,3-diferrocenyl-1-methylthioprop-1-ene (10)]. 3-Cyano-imino-1,2-diferrocenylcyclopropene (8) reacts with hydrazine to form 3-amino-6-ferrocenyl-5-ferrocenylmethyl-1,2,4-triazine (12) and Z-2,3-diferrocenylacrylohydrazide N-cyanoimide (13) as a result of intramolecular transformations. The structures of the compounds obtained were determined by IR, 1H- and 13C-NMR spectroscopy and mass spectrometry. The structures of compounds 7a and 10 were additionally confirmed by their X-ray diffraction analysis data.

Keywords

• diferrocenylcyclopropenylium salts
• cyanoamino(diferrocenyl)cyclopropenes
• [amino(cyanoimino)methyl]-1
• 2-diferrocenylethenes
• 3-amino-6-ferrocenyl-5-ferrocenyl-methyl-1
• 2
• 4-triazine