Metallation of macrocycles with 2,4-dicarbonyl-metal complexes

C - Chemistry – Metallurgy – 07 – F

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C07F 5/00 (2006.01) A61K 49/06 (2006.01) C07D 487/22 (2006.01) C07F 19/00 (2006.01)

Patent

CA 2299434

A method has been developped which utilizes a metal-2,4-dicarbonyl complex as an organic solvent soluble metal ion source in the metallation of polyazamacrocycles including porphyrins, expanded porphyrins and porphyrinoid compounds. Use of a metal ion source which is soluble in the metallation reaction medium produces significantly higher yields of a measurably purer product than is achieved using an insoluble or only sparingly soluble metal salt as in the prior art. Additionally, because the metallation can be performed in relatively concentrated mixtures, the reaction times are dramatically shorter and the amount of waste produced is less than when simple metal salts serve as the metal ion source. Further, use of the soluble metal- 2,4-dicarbonyl complex simplifies the purification protocol required for the metallated expanded porphyrin.

L'invention porte sur un procédé utilisant un complexe métal-2,4-dicarbonyle comme source d'ions métal soluble dans un solvant organique pour la métallation de polyazamacrocycles y compris des composés de porphyrine, de porphyrine expansée et de porphyrinoïde. L'utilisation d'une source d'ions métal soluble dans un milieu réactif de métallation procure des rendements nettement plus élevés en produits à pureté mesurable que celle des sels métalliques insolubles ou faiblement solubles des techniques antérieures. De plus, la métallation se faisant dans des mélanges relativement concentrés, les temps de réaction sont fortement réduits et la quantité de déchets produits est moindre qu'avec de simples sels métalliques comme source d'ions métal. En outre, l'emploi du complexe métal-2,4-dicarbonyle soluble simplifie le processus de purification nécessaire pour la porphyrine métallatée expansée.

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