Manipulation of Vinyl Groups in Protoporphyrin IX: Introduction of Deuterium and Carbon-13 Labels for Spectroscopic Studies

Using commercially available hemin (5) as the starting material, routes for preparation of monovinyl deuterated (27), monovinyl carbon-13 enriched (41, 42), and divinyl carbon-13 enriched (43, 44) derivatives of protoporphyrin IX dimethyl ester (1) are described. The monovinyl carbon-13 enriched porphyrins 41 and 42 were obtained by way of a previously reported Wittig reaction on Spirographis and iso-Spirographis porphyrin dimethyl esters 28 and 39, respectively. A new efficient partial synthesis of Spirographis porphyrin dimethyl ester (28) from deuteroporphyrin IX dimethyl ester (7) is reported, and in this the key formyl group at the 2 position is inserted by way of a Vilsmeier reaction employing a hindered amide. © 1983, American Chemical Society. All rights reserved