Über die Einwirkung von Ozon auf Porphyrine. 1. Mitteilung.

β‐Alkyloxazolochlorins: Revisiting the Ozonation of Octaalkylporphyrins, and Beyond

“…1%)o zone streams over short time spans converted etioporphyrin I( and select otherp orphyrinsw ith saturated b-substitutents) into chlorin-like chromophores with an intensified l max band at around6 50 nm (l max for octaethylporphyrin (OEP), for example, is at 622 nm). [19,20] The spectroscopic findings were suggestive of the attack of ozone on the b,b'-bonds of the porphyrin.B ased on elementala nalyses of the reluctantly crystallizing compounds, the formation of mono-, di-,a nd triozonidesw as proposed, but their structures couldn ot be further specified. [20][21][22] Intriguedb yt he Fischera nd Deželić report, [20] we decided to reinvestigate the ozonation of b-alkylporphyrins.…”

“…[19,20] The spectroscopic findings were suggestive of the attack of ozone on the b,b'-bonds of the porphyrin.B ased on elementala nalyses of the reluctantly crystallizing compounds, the formation of mono-, di-,a nd triozonidesw as proposed, but their structures couldn ot be further specified. [20][21][22] Intriguedb yt he Fischera nd Deželić report, [20] we decided to reinvestigate the ozonation of b-alkylporphyrins. After all, the ozonation and osmylation of double bonds are mechanistically related [3+ +2] cycloadditions of neutral and strongly oxidizing species.…”

Pyrrole‐Modified Subporphyrins Bearing a Sulfur‐Containing Heterocyclic Unit

“…Replacement of pyrrole rings in a porphyrin framework with non‐pyrrolic units is often a powerful means to create novel porphyrin analogues called as pyrrole‐modified porphyrins (PMPs) . The chemistry of PMPs started by the synthesis of oxazolochlorin by Fischer and Malden in 1933 . Crossley et al .…”

“…In recent years, Brückner et al . have explored various PMPs and have revealed their characteristic and intriguing structural, optical, and electrochemical properties depending on introduced modified units …”

“…[1 -3] The chemistry of PMPs started by the synthesis of oxazolochlorin by Fischer and Malden in 1933. [4] Crossley et al developed an effective synthetic route to PMPs starting from the oxidation of b-amino-tetraphenylporphyrin with various oxidants such as m-chloroperbenzoic acid (mCPBA) in 1984. [5] In recent years, Br€ uckner et al have explored various PMPs and have revealed their characteristic and intriguing structural, optical, and electrochemical properties depending on introduced modified units.…”