Generation of homologous porphyrins under simulated geochemical conditions

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Scientific paper

Crude oils generally contain at least one symmetrical homologous series of porphyrins, which is usually centered at m / e 476 (DPEP) or m / e 478 (etioporphyrin). Simulated geochemical conditions in the present study resulted in decarboxylations and alkylations which ultimately led to the synthesis of homologous porphyrins from a single porphyrin. In several series of closed tube experiments, mesoporphyrin IX dimethylester (MPDME) was mixed with a variety of constituents including benzene, acetic acid, propionic acid, water and clay; the experiments were performed at temperatures between 135°C and 400°C at time intervals up to 80 days. Dealkylation, alkylation, hydrolysis, decarboxylation and metallation products were observed. An unsymmetrical homologous series of porphyrins was produced from MPDME. The dominant mass was m / e 478 (corresponding to a double deoarboxylation). Dealkylation products in multiples of 14 amu below the m / e 478 peak comprised the other members of the series. Cu-MPDME also produced homologous porphyrins. These, however, exhibited symmetry about the dominant members, similar to the symmetry found for the porphyrins of most petroleums and oil shales.

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