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

• SUZUKI, Masaaki

• Saburo Neya,

• NISHIGAICHI, Yutaka

Abstract

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.

Journal

• Molecules

  Molecules 21 (252), 1-8, 2016-02-23

  MDPI

Keywords

• porphyrin
• trifluoromethyl
• alkoxycarbonyl
• solvolysis

Details

• CRID: 1050283688738489472
• NII Article ID: 120006800966
• ISSN: 14203049
• Web Site: http://ir.lib.shimane-u.ac.jp/48980
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • CiNii Articles