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1,3-dipolar cycloadditions with porphyrins

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dc.contributor.author Flemming, Jeffrey
dc.date.accessioned 2009-08-05T18:09:20Z
dc.date.available 2009-08-05T18:09:20Z
dc.date.copyright 2001 en
dc.date.issued 2009-08-05T18:09:20Z
dc.identifier.uri http://hdl.handle.net/2429/11715
dc.description.abstract The objective of this work is to use 1,3-dipolar cycloadditions to synthesize novel aromatic compounds based on meso-phenyl substituted porphyrins. These compounds are potential photosensitizers for use in photodynamic therapy. Tetraphenylporphyrins with a variety of substituents were reacted with selected 1,3-dipoles. Tetraphenylporphyrin (TPP), 5,10-diphenylporphyrin (DPP), and tetrakis(pentafluorophenyl)porphyrin (pFTPP) were used in reactions with azomethine ylides, carbonyl ylides, diazoalkanes, nitrile oxides, thiocarbonyl ylides, nitrile ylides, and ozone, with varying results. Centrally metallated porphyrins were also used. Azomethine ylides reacted with pFTPP efficiently giving cycloadducts of pFTPP. Three n-substituted azomethine ylides (R = benzyl, 3,5-dimethoxybenzyl, and propyl) were used. The different substituents on the pyrrolidine ring did not affect the ultra-violet / visible (UV-Vis) spectra of the chlorin. Carbonyl ylides form cycloadducts with both TPP and pFTPP. The electron deficient pFTPP reacts with non-stabilized carbonyl ylides, while TPP reacts with the electron deficient tetracyano-substituted carbonyl ylide. These results highlight the differences in reactivity of these two porphyrins. The cyano groups of 42 were hydrolyzed with concentrated hydrochloric acid, and then methylated giving 41. Changes were observed in the UV-Vis spectra as the substituents were modified. Diazomethane gave the cycloadduct pyrazoline with pFTPP (45). Compound 45 was then subjected to heat or light, both of which caused the loss of N₂ giving the cyclopropane 46. The UV-Vis a spectrum of the cyclopropane derivative was red-shifted as compared to the pyrazoline, possibly by distortion in the porphyrin ring system as a result of the cyclopropane ring. en
dc.format.extent 4788319 bytes
dc.format.mimetype application/pdf
dc.language.iso eng en
dc.relation.ispartofseries UBC Retrospective Theses Digitization Project [http://www.library.ubc.ca/archives/retro_theses/]
dc.title 1,3-dipolar cycloadditions with porphyrins en
dc.type Electronic Thesis or Dissertation
dc.degree.name Master of Science - MSc en
dc.degree.discipline Chemistry en
dc.degree.grantor University of British Columbia
dc.date.graduation 2001-11 en
dc.degree.campus UBCV en


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