Tetraphenylporphine (TPP) and its para-methyl derivative
have been synthesized by direct reaction of pyrrole with the corresponding aldehyde. The synthesis of two unsymmetrically substituted tetraarylporphyrins is reported.
The compounds prepared are' 5-(4-hydroxypheny1) -10,15,20-tritolyIporphyrin and 5-(4-hydroxypheny1)-10, 15,20-triphenyIporphyrin.
The sy thesis of covalently linked porphyrin dimers, joined via ether linkages, is described. High yields of
the tetraaryIporphyrin dimers were obtained by the reaction
of the bi-functional1,6-ditosyloxyhexane with phenolic porphyrins such as 5-(4-hydroxypheny1)-10,15,20-tritoly1-porphyrin. The dimeric porphyrins were then chromatographically separated from the unreacted monomericLporphyrins. The reduction of the porphyrins(monomers and dimers) has been carried out using the standard diimide precursor, p-toluenesulfonylhydrazine. We have been able to demonstrate
that the most efficient chlorin preparation involves
the diimide reduction of a tetraaryIporphyrin to the corresponding bacteriochlorin, followed by the addition
of the "high potential quinone" DDQ, to dehydro-genate the bacteriochlorin. A detailed study of the absorption spectra of these chlorins and bacteriochlorins was undertaken. Zinc metallo-derivatives of the porphyrins, chlorins and bacteriochlorins were prepared by the reaction of the free bases with zinc acetate in dry pyridine.
An attempt was made to synthesize tetra-meso-[p, p ' - ( 3, 3 '-phenoxypropoxypheny1)]-strati-bis porphyrin (Compound XX), a novel cyclophane system composed of two opposed, co-axial porphyrin rings, rigidly held together by peripheral ether linkages. The synthesis was attempted by construction of a second porphyrin ring on top of a pre-existing one, by way of the condensation of four pyrroles with a tetraaldehyde, derivative of tetraphenyl-porphyrin, under high dilution conditions. The last reaction step was unsuccessful. The structures and purity of the intermediate compounds leading to the strati-bis-porphyrin were established by mass spectroscopy and proton n.m.r. spectroscopy. / Science, Faculty of / Chemistry, Department of / Unknown
| Identifer | oai:union.ndltd.org:UBC/oai:circle.library.ubc.ca:2429/21765 |
| Date | January 1979 |
| Creators | Zingoni, Jesmael P. |
| Source Sets | University of British Columbia |
| Language | English |
| Detected Language | English |
| Type | Text, Thesis/Dissertation |
| Rights | For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use. |
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