| アイテムタイプ |
学術雑誌論文 / Journal Article(1) |
| 公開日 |
2025-10-24 |
| タイトル |
|
|
タイトル |
レーザー同期時間分解ESR法を用いたC=S二重結合へのラジカル付加反応素過程の観測 |
|
言語 |
ja |
| 言語 |
|
|
言語 |
jpn |
| 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 |
加藤 将利
稲葉 喬
川井 葉子
三宅 祐輔
中西 郁夫
河合 明雄
|
| 抄録 |
|
|
内容記述タイプ |
Abstract |
|
内容記述 |
A time-resolved (TR-) ESR method was applied to observe an elementary process of radical addition reaction to C=S double bond of the reversible addition fragmentation chain transfer (RAFT) polymerization regent, (thiobenzoylthio)acetic acid. As for the radical, 1-hydroxycyclohexyl (Hy-CyH) which is easily prepared by UV laser photodissociation of an aromatic ketone compound was examined. Time evolution of TR-ESR spectra in the reaction system of Hy-CyH and (thiobenzoylthio)acetic acid shows prompt generation of Hy-CyH after UV laser photolysis followed by the clear appearance of the adduct radical with a new bond formation at S atom of at C=S group in RAFT regent. TR-ESR spectrum of the adduct radical was analyzed according to the hyperfine coupling constants obtained by the DFT calculation. Although the spectrum was broad and shows no clear hyperfine structure, the bandwidth of the spectrum was reproduced by the theoretical simulation spectrum. The g value of the adduct radical was larger than that of Hy-CyH which is conventional organic free radical. This agrees well with the electronic structure of the adduct radical with two S atoms neighboring to the C atom that has the unpaired electron. Namely, a large spin-orbit coupling of the two S atoms gives rise to higher g value than Hy-CyH. Addition reaction rate of Hy-CyH and RAFT regent was estimated by the time evolution of TR-ESR spectra. |
| 書誌情報 |
Science Journal of Kanagawa University
巻 36,
p. 33-38,
発行日 2025-07
|
| DOI |
|
|
|
識別子タイプ |
DOI |
|
|
関連識別子 |
10.24792/0002001841 |
