AI Article Synopsis
- The oxidation of meso-tetraarylporphyrins produces bilitrienones when treated with sodium nitrite, trifluoroacetic acid, and air oxygen.
- The presence of para-nonyl groups in the dodecasubstituted porphyrins stabilizes the bilitrienone structure, as confirmed by X-ray crystallography.
- Without these para-nonyl groups, the bilitrienone rapidly converts to biladienone due to hydration, affecting the main product yield and subsequent isomerization.
Article Abstract
The structure of the ring-opened product from direct oxidation of meso-tetraarylporphyrins has been controversial for three decades. Herein we show that bilitrienones 2 are obtained from oxidation of metal-free dodecasubstituted porphyrins 1 in the presence of sodium nitrite, trifluoroacetic acid and air oxygen. The presence of the para-nonyl groups in 1b stabilized the corresponding bilitrienone 2b, which was characterized by X-ray crystallography. In the absence of the para-nonyl groups bilitrienone 2a undergoes a rapid hydration reaction, giving biladienone 3a as the major isolated product. The molecular structures of 2b and 3a, and. the photochemical isomerization of 3a are discussed.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2904984 | PMC |
| http://dx.doi.org/10.1016/j.tet.2009.10.098 | DOI Listing |
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