Generation of homologous porphyrins under simulated geochemical conditions |
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Authors: | Daniel J Casagrande Gordon W Hodgson |
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Institution: | Governors State University, College of Environmental and Applied Sciences, Park Forest South, Illinois, U.S.A.;The University of Calgary, Calgary, Alberta, Canada |
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Abstract: | 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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