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Partial synthesis of porphyrin S411 from protoporphyrin IX DME Sivasothy, Ramani

Abstract

This study describes the partial synthesis of porphyrin SA11 (la) from protoporphyrin IX DME (32). Conversion of 2-(2-hydroxyethyl)-A-(2-methoxycarbonylvinyl)-deuteroporphyrin IX DME (Alb) into hardero-porphyrin (3Aa) is also outlined. Photo-oxidation of (32) gives the isomeric photoprotoporphyrins (36a) and (36b); these isomers can be separated by column chromatography. Compounds (36a) and (36b) are transformed into the mono-formyl-mono-vinyl-deuteroporphyrins (33a) and (33b) by reduction with borohydride followed by the cleavage of the resulting glycols with periodate. Treatment of (33a) and (33b) with 2 equivalents of thallium(III) nitrate in methanol affords the mono-acetal-mono-formyl derivatives which, on condensation with malonic acid in the presence of piperidine gives the mono-acetal-mono-acrylie acid-deuteroporphyrins. The mono-acetal-mono-acrylic acid derivatives are converted into the corresponding mono-acrylic acid mono-(2-hydroxyethyl)-deuteroporphyrins (Ala) and (Alb) by hydrolysis and reduction with borohydride. Treatment of (Ala) with CBr^/Ph-jP affords the 2-bromoethyl derivative (A2a) which, is converted into the corresponding 2-cyanoethyl derivative (A3) by cyanide in 1-methylpyrrolidone. Compound (A3) is transformed into porphyrin SA11 (la) by methanolysis. Hydrogenation of the acrylic acid side-chain of compound (Alb) followed by the dehydration of the 2-hydroxyethyl side-chain effect's the conversion of compound (A5) into harderoporphyrin (3Aa).

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