15295-27-9Relevant articles and documents
Synthesis of fluorine analogs of protoporphyrin potentially useful for diagnosis and therapy of cancer. IV. Synthesis of (trifluorovinyl)vinyland (1-chloro-2,2-difluorovinyl)vinyldeuteroporphyrins
Shigeoka, Tsuyoshi,Kuwahara, Yasuhisa,Watanabe, Kiyoko,Sato, Kazuyuki,Omote, Masaaki,Ando, Akira,Kumadaki, Itsumaro
, p. 1326 - 1329 (1999)
Trifluoro or chlorodifluoro analogs of protoporphyrin, the compounds in the title, were synthesized for use in the diagnosis and therapy of cancer. 3- Or 8-acetyldeuteroporphyrin dimethyl esters (2 and 3) were iodinated with iodine in the presence of potassium carbonate to the corresponding iodo compounds (5 and 6). The iodo compounds (5 and 6) were treated with bis(trifluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)palladium to give trifluorovinyl derivatives (7 and 8) in good yields. Reduction of the acetyl group of 7 and 8 with sodium borohydride afforded the corresponding hydroxyethyl derivatives (9 and 10). Compounds (9 and 10) were dehydrated with methanesulfonyl chloride and triethylamine to give (trifluorovinyl)vinyldeuteroporphyrin dimethyl esters (11 and 12). Treatment of 5 and 6 with bis(1-chloro-2,2-difluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)palladium, followed by similar reactions as above gave (1-chloro-2,2-difluorovinyl)vinyldeuteroporphyrin dimethyl esters (17 and 18).
PARTIAL SYNTHESES OF 1- AND 3-METHYL DEUTERIATED DERIVATIVES OF PROTOPORPHYRIN-IX FROM PROTOHEMIN
Smith, Kevin M.,Leung, Hiu-Kwong,Parish, Daniel W.
, p. 2743 - 2761 (2007/10/02)
Treatment of 2,4-diacetyldeuteroporphyrin-IX dimethyl ester (3) with sodium methoxide in methanol-d affords the 1,3-di-(trideuteriomethyl) derivative in which the acetyl methyls and propionate methylenes adjacent to the ester carbonyl have also been deuteriated.The acetyl methyls and propionates can be back-exchanged under acidic conditions, but the 1- and 3-methyls retain their isotope labeling.Reduction with sodium borohydride, followed by dehydration affords the corresponding 1,3-di-(trideuteriomethyl)-protoporphyrin-IX dimethyl ester (4) with approximately 95percent deuteriation in the methyls.Insertion of iron and hydrolysis affords the corresponding hemin (15), suitable for n.m.r. studies of reconstituted heme proteins.A similar sequence of reactions with 2- and 4- monoacetyldeuteroporphyrins (5) and (6) gives the 1- and 3-(trideuteriomethyl) derivatives and these are, in turn, further acetylated and transformed into the corresponding mono-trideuteriomethylprotoporphyrins (7) and (8), and hemins (22) and (23).
