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Porphyrins which contain 1-hydroxy(alkoxy)ethyl or alkoxymethyl substituents on the periphery of the macrocycle (i.e. formally able to yield “benzyl type” carbocations) react with nucleophiles (4-tert-butylphenol or the β-diketones acetylacetone, benzoylacetone, dibenzoylmethane, or 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione) in the presence of excess zinc acetate. They give high yields of the corresponding addition products, which are the zinc complexes of porphyrins with a 1-(4-tert-butylphenoxy)ethyl substituent or with substituents containing β-diketone residues.