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Molecules 2016, 21(3), 252;

Synthesis of 5,10-bis(Trifluoromethyl) Substituted β-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups

Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060, Nishikawatsu-cho, Matsue, Shimane 690-8504, Japan
Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1, Inohana, Chuo-ku, Chiba 260-8675, Japan
Author to whom correspondence should be addressed.
Academic Editors: M. Graça P. M. S. Neves and M. Amparo F. Faustino
Received: 9 January 2016 / Revised: 15 February 2016 / Accepted: 19 February 2016 / Published: 23 February 2016
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5,10-Bistrifluoromethyl substituted β-octamethylporphyrins were synthesized via a scrambling side reaction of a dipyrromethane precursor in the presence of a large excess of trifluoroacetic acid. Compared with the trans-analogs, the cis-analogs of meso-trifluoromethyl β-octaalkylporphyrin showed more red-shifted absorption bands. These meso-trifluoromethyl derivatives of β-octaalkylporphyrins underwent smooth metalation, similar to other common porphyrins, however, the corresponding zinc complexes underwent a type of solvolysis, whereby the trifluoromethyl groups were converted into methoxycarbonyl groups by the methanol used as solvent. UV-visible absorption spectra and X-ray crystal structure analyses revealed that the presence of a methoxycarbonyl substituent did not influence the deformation of the molecular framework and its absorption properties; this is because the methoxycarbonyl has a planar and perpendicular geometry, as opposed to the relatively bulky trifluoromethyl substituent. View Full-Text
Keywords: porphyrin; trifluoromethyl; alkoxycarbonyl; solvolysis porphyrin; trifluoromethyl; alkoxycarbonyl; solvolysis

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Suzuki, M.; Neya, S.; Nishigaichi, Y. Synthesis of 5,10-bis(Trifluoromethyl) Substituted β-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups. Molecules 2016, 21, 252.

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