The two-step mechanochemical synthesis of porphyrins

• Published in: Faraday discussions Vol. 170; pp. 59 - 69
• Main Authors: Shy, Hannah, Mackin, Paula, Orvieto, Andrea S, Gharbharan, Deepa, Peterson, Geneva R, Bampos, Nick, Hamilton, Tamara D
• Format: Journal Article
• Language: English
• Published: England 01.01.2014
• Subjects: Benzaldehyde; Benzaldehydes - chemistry; Mechanochemistry; Oxidation; Oxidation-Reduction; Porphyrins; Porphyrins - chemical synthesis; Pyrroles; Pyrroles - chemistry; Solvents; Synthesis; Synthesis (chemistry)
• ISSN: 1359-6640; 1364-5498
• DOI: 10.1039/C3FD00140G

Porphyrin synthesis under solvent-free conditions represents the "greening" of a traditional synthesis that normally requires large amounts of organic solvent, and has hindered the industrial-scale synthesis of this useful class of molecules. We have found that the four-fold acid-catalysed condensation of aldehyde and pyrrole to yield a tetra-substituted porphyrin is possible through mechanochemical techniques, without a solvent present. This represents one of the still-rare examples of carbon-carbon bond formation by mechanochemistry. Specifically, upon grinding equimolar amounts of pyrrole and benzaldehyde in the presence of an acid catalyst, cyclization takes place to give reduced porphyrin precursors (reversible), which upon oxidation form tetraphenylporphyrin (TPP). The approach has been found to be suitable for the synthesis of a variety of meso-tetrasubstituted porphyrins. Oxidation can occur either by using an oxidizing agent in solution, to give yields comparable to those published for traditional methods of porphyrin synthesis, or through mechanochemical means resulting in a two-step mechanochemical synthesis to give slightly lower yields that are still being optimized. We are also working on "green" methods of porphyrin isolation, including entrainment sublimation, which would hopefully further reduce the need for large amounts of organic solvent. These results hold promise for the development of mechanochemical synthetic protocols for porphyrins and related classes of compounds.