ヘム酸化酵素反応をモデルにしたポルフィリンの共役酸化反応のメカニズムや置換基効果について検討し、リニアテトラピロールやオキサポルフィリンなどのテトラピロール誘導体の新しい合成方法を確立した。テトラピロール誘導体の反応性や物性に関しても検討し、オキサポルフィリン亜鉛錯体が蛍光を示すことや、フェノキシ基をもつリニアテトラピロールが金属イオンと反応することでオキサポルフィリンに変換される反応などを見出した。 / Coupled oxidation of [tetraarylporphyrinato]iron(III) chloride was studied with particular attention on the mechanism, substituent effects, and reactivity of the resulting linear tetrapyrroles. Meso-substituted bilindione was converted into oxaporphyrin zinc complex by refluxing it with zinc acetate and acetic anhydride. Oxaporphyrin zinc complexes showed characteristic fluorescence emission at 657 nm. Oxaporphyrin zinc complexes were reacted with various nucleophiles such as alcohol, amine, thiol and enolate to give linear tetrapyrroles. Moreover, linear tetrapyrroles having a phenoxy group were spontaneously converted to oxaporphyrin metal complexes upon addition of metal acetates. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University
Identifer | oai:union.ndltd.org:doshisha.ac.jp/oai:doshisha.repo.nii.ac.jp:00001158 |
Date | 22 March 2014 |
Creators | 掛谷 和久, Kazuhisa Kakeya |
Source Sets | Doshisha University |
Language | Japanese |
Detected Language | English |
Type | Thesis or Dissertation |
Format | application/pdf |
Source | https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB12863852/?lang=0 |
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