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Synthesis of p -substituted tetraphenylporphyrins and corresponding ferric complexes
with mixed-solvents method |
Zhicheng SUN1,Yuanbin SHE1,Rugang ZHONG2, |
1.Institute of Green Chemistry
and Fine Chemicals, Beijing University of Technology, Beijing 100124,
China; 2.College of Life Science
& Bioengineering, Beijing University of Technology, Beijing 100124,
China; |
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Abstract By using mixed-solvents method, five kinds of p-substituted tetraphenylporphyrin compounds [T(p-R)PPH2, R=NO2, Cl, CH3, OCH3, OH] were synthesized by the condensation of p-substituted benzaldehyde with pyrrole in mixed solvents (propionic acid, acetic acid and nitrobenzene), and corresponding ferric complexes [T(p-R)PPFeIIICl] were synthesized in dimethylformamide. The above free base porphyrins were obtained in 30%–50% yields, metalation yields were up to 90% and total yields of ferric complexes were 27%–50%. Effects of reactive conditions, solvents and oxidants on yields of free base porphyrins were investigated and the relevant mechanism was discussed. Structures of the above porphyrin complexes were characterized by ultraviolet-visible (UV-Vis), infrared (IR) and far infrared (FIR) spectroscopy.
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Issue Date: 05 December 2009
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Haber J, Matachowski L, Pamin K, Poltowicz J. Theeffect of peripheral substituents in metalloporphyrins on their catalyticactivity in Lyons system. J Mol Catal AChem, 2003, 198(1―2): 215―221
doi: 10.1016/S1381-1169(02)00688-X
|
|
Tagliatesta P, Pastorini A. Remarkable selectivity inthe cyclopropanation reactions catalysed by an halogenated iron meso-tetraphenylporphyrin. J Mol Catal A Chem, 2003, 198(1―2): 57―61
doi: 10.1016/S1381-1169(02)00698-2
|
|
Zakharieva O, Trautwein A X, Veeger C. Porphyrin-Fe(III)-hydroperoxide and porphyrin-Fe(III)-peroxideanion as catalytic intermediates in cytochrome P450-catalyzed hydroxylationreactions: a molecular orbital study. BiophysicalChemistry, 2000, 88(1―3): 11―34
|
|
Davydov R, Makris T M, Kofman V, Werst D E, Sligar S G, Hoffman B M. Hydroxylation of camphor by-reduced oxy-cytochrome P450cam: Mechanisticimplications of EPR and ENDOR studies of catalytic intermediates innative and mutant enzymes. J Am Chem Soc, 2001, 123(7): 1403―1415
doi: 10.1021/ja003583l
|
|
Guo C C, Liu Q, Wang X T, Hu H Y. Selectiveliquid phase oxidation of toluene with air. Applied Catalysis A-General, 2005, 282(1―2): 55―59
doi: 10.1016/j.apcata.2004.11.045
|
|
Yuan Y, Ji H B, Chen Y X, Han Y, Song X F, She Y B, Zhong R G. Oxidation of cyclohexaneto adipic acid using Fe-porphyrin as a biomimetic catalyst. Org Process Res Dev, 2004, 8(3): 418―420
doi: 10.1021/op049974s
|
|
Wang L Z, She Y B, Zhong R G, Ji H B, Zhang Y H, Song X F. A green process for oxidation of p-nitrotoluene Catalyzed by metalloporphyrins under mild conditions. Org Process Res Dev, 2006, 10(4), 757―761
doi: 10.1021/op060056z
|
|
Zhang R, Horner J H, Newcomb M. Laser flash photolysis generation and kinetic studiesof porphyrin-manganese-oxo intermediates. Rate constants for oxidationseffected by porphyrin-MnⅤ-oxo species andapparent disproportionation equilibrium constants for porphyrin-MnⅣ-oxo species. J Am ChemSoc, 2005, 127(18): 6573―6582
doi: 10.1021/ja045042s
|
|
She Y B, Feng L S, Wang A X, Li X Y. Synthesisof substituted μ-oxo-bis[tetra-phenylporphyrinatoiron] compounds from free base porphyrins by a one–potmethod. Chin J Chem Eng, 2008, 16(3): 369―372
doi: 10.1016/S1004-9541(08)60090-7
|
|
Geier G R, Ciringh Y Z, Li F R, Haynes D M, Lindsey J S. Two-step, one-flask synthesesof meso-substituted porphyrinicmacrocycles. Org Lett, 2000, 2(12): 1745―1748
doi: 10.1021/ol005917h
|
|
Sharada D S, Muresan A Z, Muthukumaran K M, Lindsey J S. Direct synthesis of palladium porphyrins from acyldipyrromethanes. J Org Chem, 2005, 70(9): 3500―3510
doi: 10.1021/jo050120v
|
|
Adler A D, Longo F R, Shergalis W. Mechanistic investigations of porphyrin syntheses. I.Preliminary studies on ms-tetraphenylporphin. J Am Chem Soc, 1964, 86(15): 3145―3149
doi: 10.1021/ja01069a035
|
|
Sun Z C, She Y B, Li X Y, Yu Y M, Zhong R G. Synthesis of Tetraphenylporphyrin andits influent factors. Chin J Appl Chem, 2007, 24(suppl): 584―586
|
|
Kristine P, Thomas G S. Core expansion, ruffling,and doming effects on metalloporphyrin vibrational frequencies. J Am Chem Soc, 1992, 114(10): 3793―3801
doi: 10.1021/ja00036a031
|
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