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Asymmetric photolysis of 2-phenylcycloalkanones with circularly polarized light: A kinetic model for magnetic field effects
http://hdl.handle.net/2297/38273
http://hdl.handle.net/2297/38273431e5dfc-a4e0-4923-add1-513aa7ec7e98
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
PH-PR-NAKAGAKI-R-1223.pdf (797.2 kB)
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| Item type | 学術雑誌論文 / Journal Article(1) | |||||
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| 公開日 | 2017-10-04 | |||||
| タイトル | ||||||
| タイトル | Asymmetric photolysis of 2-phenylcycloalkanones with circularly polarized light: A kinetic model for magnetic field effects | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
| 資源タイプ | journal article | |||||
| 著者 |
Kohtani, Shigeru
× Kohtani, Shigeru× Sugiyama, Masahide× Fujiwara, Yoshihisa× Tanimoto, Yoshifumi× Nakagaki, Ryoichi |
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| 書誌情報 |
Bulletin of the Chemical Society of Japan 巻 75, 号 6, p. 1223-1233, 発行日 2002-01-01 |
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| ISSN | ||||||
| 収録物識別子タイプ | ISSN | |||||
| 収録物識別子 | 0009-2673 | |||||
| NCID | ||||||
| 収録物識別子タイプ | NCID | |||||
| 収録物識別子 | AA00580132 | |||||
| DOI | ||||||
| 関連タイプ | isIdenticalTo | |||||
| 識別子タイプ | DOI | |||||
| 関連識別子 | 10.1246/bcsj.75.1223 | |||||
| 出版者 | ||||||
| 出版者 | The Chemical Society of Japan = 日本化学会 | |||||
| 抄録 | ||||||
| 内容記述タイプ | Abstract | |||||
| 内容記述 | Magnetic field effects (MFE) on asymmetric photolysis involving a biradical intermediate have been investigated on a kinetic model where an intersystem crossing (ISC) of the intermediate is taken into account. Changes in the enantiomeric excesses (ee) of chiral substances with circularly polarized light (CPL) irradiation have been simulated, and the necessary conditions for observing the MFE were obtained. The asymmetric photolysis of racemic 2-phenylcycloalkanones (2-PCAs) with CPL has been carried out in both the presence and absence of a magnetic field. Since the anisotropy g factors of 2-PCAs are considerably large, the CPL-induced ee are achieved to a few percent after 90% decomposition though the MFE are not observed. The photolysis mechanism of 2-PCAs in an air-saturated solution has been also clarified. Triplet acyl–benzyl biradicals, formed via photochemical α-cleavage of 2-PCAs, react with O2 dissolved in the solution and result in the formation of acetophenone and alkenoic acids. The bimolecular reactions are diffusion-controlled and the rates are comparable to those of ISC to the singlet biradicals for all 2-PCAs. The recombination yields of the biradicals are sufficiently large. However, the biradical ISC rate shows little magnetic field dependence, which explains the absence of the MFE in this asymmetric photolysis. | |||||
| 権利 | ||||||
| 権利情報 | Copyright © The Chemical Society of Japan 日本化学会 | |||||
| 著者版フラグ | ||||||
| 出版タイプ | VoR | |||||
| 出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||
| 関連URI | ||||||
| 識別子タイプ | URI | |||||
| 関連識別子 | https://www.jstage.jst.go.jp/browse/bcsj | |||||
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| 識別子タイプ | URI | |||||
| 関連識別子 | http://www.chemistry.or.jp/ | |||||
