Tetraphenylporphyrin synthesis

Romain L, Mien V, Karine T, Rachida Z, Vincent S, Pierre K (2008) A facile and rapid iodine-catalyzed meso-tetraphenylporphyrin synthesis using microwave activation. Tetrahedron Lett 49 5537-5539... 

Dietel E, Hirsch A, Zhou J and Rieker A 1998 Synthesis and electrochemical investigations of molecular architectures involving Cgg and tetraphenylporphyrin as building blocks J. Chem. See., Perkin Trans. 2 1357-64... 

Dye-Sensitized Photoisomerization. One technological appHcation of photoisomerization is in the synthesis of vitamin A. In a mixture of vitamin A acetate (all-trans stmcture) and the 11-cis isomer (23), sensitized photoisomerization of the 11-cis to the all-trans molecule occurs using zinc tetraphenylporphyrin, chlorophyU, hematoporphyrin, rose bengal, or erythrosin as sensitizers (73). Another photoisomerization is reported to be responsible for dye laser mode-locking (74). In this example, one metastable isomer of an oxadicarbocyanine dye was formed during flashlamp excitation, and it was the isomer that exhibited mode-locking characteristics. 

A more general synthesis of selenophene derivatives, starting from diacetylenes and sodium hydrogen selenide, was investigated by Curtis.48 In the synthesis of new tetraphenylporphyrin molecules containing heteroatoms other than nitrogen, Ulman et al.49 used in principle the method of Curtis for the synthesis of the starting material (17). 

Extension of the 1,3-DC approach to the synthesis of novel pyrazoline-fused chlorin 78 by the reaction of P-nitro-meso-tetraphenylporphyrin le with diazomethane has also been explored by Cavaleiro and co-workers (Scheme 27) <02S 1155>. The resulting chlorin 78 could be further converted into the pyrazole-fused porphyrin 79 by treatment with DBU or into the methanochlorin 80 by refluxing in toluene. 

A simple and rapid synthesis of tetrapyrrolic macrocycle has been achieved under dry media conditions with microwave activation. Pyrrole and benzaldehyde adsorbed on silica gel afford tetraphenylporphyrin within 10 min (Scheme 8.26), whereas with conventional methods (e. g. acetic acid in the presence of pyridine) 24 h were necessary. 

Design and Synthesis of Tetraphenylporphyrin-based Protein Surface... 

The structure of N-confused porphyrin 88 (Fig. 27) was first proposed in 1943 by S. Aronoff and M. Calvin (the future Nobel laureate) during a reexamination of Rothemund s synthesis of tetraphenylporphyrin [47], However, no convincing proof for such a structure was provided and only two of the six pigments isolated... 

Photo-oxidation of citronellol in polystyrene beads [120]. A sample of 3.0 g of polystyrene beads (commercial, cross-polymerized with 1% of divinylbenzene) was treated with a solution of 2 mg of tetraphenylporphyrin and 780 mg (5 mmol) of citronellol in 20 mL of ethyl acetate in a petri-dish (30 cm diameter). After 2h in a ventilated hood, the solvent has evaporated and the petri-dish was covered with a glass plate and irradiated for 5 h with a 150 W halogen lamp. The solid support was then washed with 3 x 20 mL of ethanol, the combined ethanol fractions were rota-evaporated and 900 mg of the hydroperoxide mixture (96%) was isolated as a slightly yellow oil. The hydroperoxides were quantitatively reduced to the corresponding allylic alcohols by treatment with sodium sulfite. One of these products is used in the industrial synthesis of rose oxide. 

Bonnet, S., Forano, C., de Roy, A. and Besse, J. P. (1996). Synthesis of hybrid organo-mineral materials anionic tetraphenylporphyrins in layered double hydroxides. Chem. Mater. 8, 1962. 

A novel synthesis of benzosultam 164 involves a Co-based catalytic system for intramolecular C-H animation with azides <07OL4889>. The commercially available cobalt tetraphenylporphyrin complex, Co(TPP) 163, is an effective catalyst for catalyzing C-H animation with arylsulfonyl azides 162 leading to benzosultams 164 in excellent yields. In addition to benzylic C-H bond, non-benzylic C-H bonds can also be intramolecularly aminated. For example, reaction of arylsulfonyl azides 165 with Co catalyst 163 results in a mixture of 5- and 6-membered ring products, 166 and 167. 

Four years after their initial report, the first alternative synthesis of homoporphyrins was reported by Callot and coworkers [14], In this work it was found that the reaction of zinc tetraphenylporphyrin 20 with disubstituted diazoalkanes (Scheme 6) gives, after workup, the corresponding free-base homoporphyrins, namely 21-25. Treatment of these expanded porphyrins with Ni(II) gives the corresponding nickel complexes, namely 26-30. Reactions of 21 with other metals also gives the expected metal complexes 31-34 [15-17]. 

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