825-24-1Relevant 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 (2019/09/20)
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.
COBALT(II)TETRAPORPHYRIN-CATALYZED ISOMERISATION OF ELECTRONEGATIVE SUBSTITUTED QADRICYCLANES
Miki, Sadao,Ohno, Toshinobu,Iwasaki, Hideaki,Yoshida, Zen-ichi
, p. 3487 - 3490 (2007/10/02)
Co(II)TPP-catalyzed isomerisation of a series of electronegative substituted quadricyclanes(1) to the corresponding norbornadiene(2) was found to proceed via radicophilic attack of the metal to 1.
