Porphine (2) and Metalloporphine (M-2) Synthesis. Efforts to synthesize the porphyrin macrocycle were started by Hans Fischer over a century ago. Two decades later, Rothemund's cyclocondensation procedure represented an important advance, but the yields remained extremely low. Many others contributed, and particularly noteworthy are Adler and Longo's condensation of pyrrole with an aldehyde in refluxing propionic acid and Lindsey's acid catalyzed cyclization. Although fairly successful for substituted porphyrins, these procedures yield only minimal yields of parent 2, on the order of 1 -2%. Oxidation of 2hydroxymethylpyrrole solutions with potassium persulfate affords a yield of ~5% but appears unsuitable for a preparation of larger amounts of 2. We have adopted the more recently developed procedure of Neya and Funasaki, who prepared 2 by thermal removal of meso substituents from protonated meso-tetrakis(tbutyl)porphyrin and meso-tetrakis(n-hexyloxycarbonyl)porphyrin (3) 3 in ~75% yield. These meso substituted porphyrins have been reported to form in yields of ~15% from readily available starting materials (Scheme 1). Unfortunately, in our hands the yields of 3 prepared according to the published procedure fluctuated considerably and never exceeded ~10% (based on di-nhexyl tartrate). They were even lower when the alkyl R was n-butyl or n-octyl instead of n-hexyl. The modified procedure developed presently reliably converts di-n-hexyl tartrate into 2 in an overall yield of 10 -15%.