Tetraoxaporphyrinogen (Tetraoxaquaterene): Oxidation to the Tetraoxaporphyrin Dication

The well known, extremely reactive [18]annulene 1 and the hypothetical isomer 2 should be capable of being stabilized by CH2‐ and CHCH‐groups as internal and external bridges, respectively. The corresponding hydrocarbons, 3 and 4, are still unknown, although they are of great interest as links betw...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Angewandte Chemie International Edition 1988-03, Vol.27 (3), p.409-411
Hauptverfasser: Haas, Wilhelm, Knipp, Bernd, Sicken, Martin, Lex, Johann, Vogel, Emanuel
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The well known, extremely reactive [18]annulene 1 and the hypothetical isomer 2 should be capable of being stabilized by CH2‐ and CHCH‐groups as internal and external bridges, respectively. The corresponding hydrocarbons, 3 and 4, are still unknown, although they are of great interest as links between the non‐natural annulenes and the porphyrin 5 or the porphycene 6 recently synthesized for the first time. It has now been possible to prepare the tetraoxa analogues of 5 and 6, i.e. the dications 7 and 8. In both cases they could be isolated as the perchlorates and structurally characterized, revealing their relationship with 5 and 6, respectively. In the synthesis of 7 the decisive step was a MacDonald condensation, followed directly by an oxidation, whereas the route to 8 led via a McMurry coupling and subsequent oxidation. Reaction of 2,2′‐difurylmethane with formaldehyde afforded tetraoxaporphyrinogen in low yield, which could be oxidized with nitric acid to the tetraoxaporphyrin.
ISSN:0570-0833
1521-3773
DOI:10.1002/anie.198804091