7399-31-7Relevant academic research and scientific papers
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.
Photochemical reactions of charge-transfer complexes. IV. The orientation effects of charge-transfer complexes: theory and experiment
Wong, Po Cheong,Arnold, Donald R.
, p. 982 - 989 (2007/10/02)
In paper number III of this series (2) ab initio and PCILO molecular orbital calculations for the four ?-?* charge-transfer (ct) complexes formed between maleonitrile (MN) and fumaronitrile (FN), and cis (CS) and trans-1,2-dimethoxyethylene (TR) were reported.This paper reports the ct transition absorption characteristics and association constans of these complexes as a function of temperature.From this data the heats of formation of the complexes are determined and these experimental results are then compared with the theoretical values; good agreement is obtained.The order of complex stability ( (kcal mol)) measured in chloroform solution is: MN-TR(0.55) FN-TR(0.65) MN-CS(0.78) FN-CS(1.25) we reach the conclusion that for these complexes orientation effects of the substituents are quite small in magnitude and that the dominant factor influencing complex stability follows the redox potential difference.The structures of the complexes are discussed in view of these results.
