950914-46-2Relevant academic research and scientific papers
Dimethoxytetraphenylbenziporphyrins
Szymanski, Joseph T.,Lash, Timothy D.
, p. 8613 - 8616 (2003)
A two step synthesis of dimethoxytetraphenylbenziporphyrins is reported. Although these porphyrin analogues are cross-conjugated, addition of TFA affords diprotonated species that show a significant diamagnetic ring current. In addition, reaction with nickel(II) acetate also affords organometallic derivatives with borderline aromatic characteristics.
Synthesis and metalation of dimethoxybenziporphyrins, thiabenziporphyrins, and dibenziporphyrins
Fosu, Stacy C.,Ferrence, Gregory M.,Lash, Timothy D.
, p. 11061 - 11074 (2014)
Dimethoxybenzitripyrranes were prepared in excellent yields by reacting benzene dicarbinols with BF3·Et2O and excess pyrrole in refluxing 1,2-dichloroethane. Reaction with a pyrrole dialdehyde in the presence of TFA, followed by oxidation with DDQ, afforded good yields of meso-diphenyldimethoxybenziporphyrins. These dimethoxyporphyrinoids exhibited weakly diatropic properties that were enhanced upon protonation. The dimethoxybenzitripyrranes also reacted with a thiophene dicarbinol to give dimethoxythiabenziporphyrins, and the nonplanar nature of this system was demonstrated by X-ray crystallography. The dimethoxybenziporphyrins reacted with palladium(II) acetate to give the related organometallic derivatives, but the thiabenziporphyrins underwent a demethylation to afford palladium(II) thiaoxybenziporphyrins. Related palladium(II) complexes were also prepared from previously reported thiacarbaporphyrinoids. The X-ray structure for one of the complexes showed that the six-membered ring is very distorted and the thiophene ring is strongly tilted out of the plane of the macrocycle. The dimethoxybenzitripyrranes also reacted with dimethoxybenzene dicarbinols to give the first examples of dibenziporphyrins, thereby further demonstrating the versatility of this synthetic methodology.
Tetraaryldimethoxybenziporphyrins. At the edge of carbaporphyrinoid aromaticity
Lash, Timothy D.,Szymanski, Joseph T.,Ferrence, Gregory M.
, p. 6481 - 6492 (2008/02/11)
(Chemical Equation Presented) A series of eight dimethoxybenziporphyrins were prepared in three steps from 1,3-dimethoxybenzene or 2,6-dimethoxytoluene. Dibromination, followed by lithium-halogen exchange and reaction with benzaldehyde gave dicarbinol int
