Hydrazinüberbrückte [14]Annulene: Eine einfache Synthese des 4,9‐Bis(diacetylamino)‐3,8‐dicyan‐10b,10c‐diaza‐dicyclopenta[ ef , kl ]heptalens

Abstract

Hydraziniiberbruckte [14]Annulene : Eke einfache Synthese des 4,9-Bis(diacetylamino)-3 ,S-dicyan-lOb ,10c-diazadicyclopent a[ ef,kZ] hep t alens 1) Eingegangen am 12. Februar 1973 N,N-Bisuccinimid (5) reagiert mit (Cyanmethylen)-bzw. (Athoxycarbonylmethy1en)triphenylphosphoran zu den 2,2',5,5'-tetrasubstituierten 1,l'-Bipyrrolen 7a, b. Kondensation von 7 a zum Enaminnitril 8 und anschlieBende dehydrierende Acetylierung fuhrt zum substituierten diatropen 10b,10c-Diazadicyclopentaheptalen 9. Hydrazine-bridged [14]Annulenes : A Simple Synthesis of 4,9-Bis(diacetylamino)-3,8-dicyano-10b,10c-diazadicyclopenta[ef,kl]heptalene 1)N,N-Bisuccinimid (5) reacts with (cyanomethy1ene)-or (iithoxycarbonylmethy1ene)triphenylphosphoram to give the 2,2',5.5'-tetrasubstituted 1,l'-bipyrrols 7a, b. Condensation of 7 a to 8 and subsequent dehydrogenating acetylation yields the diatropic title compound 9. W. Flitsch und H . YeetersJahrg. 106

Synthesis and Properties of Heterophanes

“…Flitsch and Peeters 161 have prepared the annulene 259 by the route shown in Scheme 47. Compound 259 exhibits a strong diamagnetic ring current.…”

Synthesis, oxidation and protonation of octamethyl-1,1′-bipyrrole

“…10 In addition to the oxidative coupling of alkali metal pyrrolides, 3 this method has been in use up to now. 11 We have reacted hydrazine with 3,4-dimethylhexane-2,5dione (4) to prepare 2,2Ј,3,3Ј,4,4Ј,5,5Ј-octamethyl-1,1Јbipyrrole (6). No effort has been made to isolate the 1aminopyrrole 5 which is presumably formed as an intermediate.…”

“…5 A special topic deals with the chemistry of hydrazine-bridged annulenes. 6 As part of our investigations on pyrrolyl and pyrrole metal π-complexes 7 we are interested in reductive N,N-bond fission as a route to new azacyclopentadienyl metal complexes. The properties of 2,2Ј,3,3Ј,4,4Ј,5,5Ј-octamethyl-1,1Ј-bipyrrole have been mentioned only briefly.…”

Electronic, Spectroscopic, and Ion-Sensing Properties of a Dehydro[m]pyrido[14]- and [15]annulene Isomer Library

“…We have been particularly interested in exploring the physicochemical properties of the dehydro­[ m ]­pyrido­[ n ]­annulenes, for example, 4 – 6 (Chart ), which are nitrogen-heterocyclic analogues of the dehydrobenzo­[ n ]­annulenes that are capable of binding metal ions directly to the heteroatoms situated on the outer surface of the macrocyclic ring. − Some of these and related macrocycles were discovered to function as luminescence ion sensors ,, and to afford coordination network polymers with specific metal salts . Coordination polymers incorporating dehydro­[ m ]­pyrido­[ n ]­annulene repeat units, which topologically mimic theoretically proposed all-carbon networks, are attractive synthetic targets because they may be expected to display a rich variety of exploitable properties such as electrochemical, photochemical, magnetic, optical, catalytic, porous, inclusion, sensory, and mechanical behavior. − …”