SYNTHESIS OF L(2,2,2-TRIFLUORO-1-HYDROXYETHYL)DEUTEROPORPHYRINS AND THEIR DERIVATIZATION TO PORPHYRIN DERIVATIVES WITH ELONGATED SIDE-CHAINS

We previously synthesized 3- and 8-mono-, and is(2,2,2-trifluoro-1-hyd roxyethyl)deuteroporphyrin dimethyl esters (2-4) by Friedel-Crafts rea ction of deuteroporphyrin dimethyl ester (1) with trifluoroacetaldehyd e, and trifluorohematoporphyrin analogs (5 and 6) by acetylation of 2 and 3 followed by reduction, These fluorine analogs of natural porphyr ins have interesting biological properties; some of them accumulate se lectively in certain tumor cells, In order to introduce larger substit uents at the 8- or 3-position of 2 and 3, 2 and 3 were converted in se veral steps to 8- and 3-formyl derivatives (13 and 14), respectively, These were treated with vinylmagnesium bromide to give 8- or 3-(1-hydr oxy-2-propenyl) derivatives (15 or 16), Further, reaction of 7 or 8 wi th the enol ether of 2-octanone gave the 8- or 3-(3-oxo-1-nonenyl) com pounds (17 or 18), The affinities of the porphyrin derivatives, obtain ed by hydrolysis of the above porphyrin esters, for tumor tissues were examined, Among them, the porphyrin obtained by hydrolysis of 16 was found to accumulate in liver cancer transplanted in nude mice to a gre ater extent than hematoporphyrin.