19005-04-0Relevant articles and documents
1-Bromo-1,2-dicyanoethylene: A dicyanoacetylene synthon useful in tetraazaporphyrin synthesis
Fitzgerald, Jeffrey P.,Korenak, John P.,Steinaker, Delano A.,Swogger, Logan M.,Lois, Jessica A.
, p. 1092 - 1099 (2019)
Dicyanoacetylene, a highly reactive dienophile, readily reacts to form substituted maleonitriles which serve as precursors to soluble tetraazaporphyrins. Unfortunately, dicyanoacetylene is difficult to synthesize in large quantities. We report here a new dicyanoacetylene synthon, 1-bromo-1,2-dicyanoethylene, which is easily made in high yield by reaction of elemental bromine with fumaronitrile and easily purified by vacuum distillation. The resulting 5:1 mixture of geometric isomers reacts with dienes via a Diels-Alder reaction followed by elimination of HBr to give substituted maleonitriles. We demonstrate the utility of these reactions by reporting the synthesis of a novel, soluble tetraazaporphyrin bearing four 1,4-fused cyclohexyl groups on the macrocycle periphery.
SYNTHESIS OF anti-SESQUINORBORNENE AND RELATED POLYCYCLIC ALKENES via REDUCTIVE ELIMINATION OF VICINAL DICYANO DERIVATIVES
Lucchi, Ottorino De,Piccolrovazzi, Nicoletta,Licini, Giulia,Modena, Giorgio,Valle, Giovanni
, p. 401 - 408 (2007/10/02)
A methodology for the preparation of both endocyclic unsaturated molecules via reductive elimination of vicinal dicyano derivatives is reported.The method is useful for the preparation of anti-sesquinorbornene and related hitherto unknown molecules starting from the respective vicinal dicyano derivatives which are readily available via Diels-Alder reactions.From a practical point of view, the best decyanation procedure for these substrates is to use finely dispersed sodium in tetrahydrofuran under sonication.The X-ray analysis of anti-1,4,4a,5,8,8a-hexahydro-1,4;5,8-dimethanonaphthalene-4a,8a-dicarbonitrile, 3, is reported.Crystal data: orthorhombic, space group P212121; Z=4; a=16.059(5), b=8.920(3), c=7.592(3) Angstroem; V=1087.5 Angstroem3, Dc=1.27 g*cm-3.
