WEKO3
アイテム
EFFECT OF SOLVENT ON PROTON TUNNELING IN THE REACTIONS OF 4-NITROPHENYLNITROMETHANE WITH 1-ETHYLPIPERIDINE AND 1,8-DIAZABICYCLO [5.4.0] UNDEC-7-ENE
https://doi.org/10.14990/00000077
https://doi.org/10.14990/00000077b8e7f206-9acb-4773-a4dc-31374ca251e0
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
K00040 (513.3 kB)
|
|
| Item type | 紀要論文 / Departmental Bulletin Paper(1) | |||||
|---|---|---|---|---|---|---|
| 公開日 | 2015-03-24 | |||||
| タイトル | ||||||
| タイトル | EFFECT OF SOLVENT ON PROTON TUNNELING IN THE REACTIONS OF 4-NITROPHENYLNITROMETHANE WITH 1-ETHYLPIPERIDINE AND 1,8-DIAZABICYCLO [5.4.0] UNDEC-7-ENE | |||||
| タイトル | ||||||
| タイトル | EFFECT OF SOLVENT ON PROTON TUNNELING IN THE REACTIONS OF 4-NITROPHENYLNITROMETHANE WITH 1-ETHYLPIPERIDINE AND 1,8-DIAZABICYCLO [5.4.0] UNDEC-7-ENE | |||||
| 言語 | en | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプ | departmental bulletin paper | |||||
| ID登録 | ||||||
| ID登録 | 10.14990/00000077 | |||||
| ID登録タイプ | JaLC | |||||
| 著者 |
Shimada, S.
× Shimada, S.× Ikeda, Y.× Sasaki, M.× SHIMADA, S.× IKEDA, Y.× SASAKI, M. |
|||||
| 抄録 | ||||||
| 内容記述タイプ | Abstract | |||||
| 内容記述 | A kinetic study has been carried out on the proton-transfer reactions from 4-nitrophenylnitromethane (4NPNM) to 1-ethylpiperidine (EP) and to 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in acetonitrile and dichloromethane by means of a stopped-flow method, the attention being focused to solvent effect on kinetic isotope effect (k_f^H/k_f^D) and degree of tunneling. For the 4NPNM-EP system, k_f^H/k_f^D at 25℃ was 17.2 and the activation energy difference, E_af^D-E_af^H, was as large as 10.8 kJmol^-, which suggested that the degree of proton-tunneling was significant. On the contrary, for the 4NPNM-DBU system the degree of proton-tunneling in both acetonitrile and dichloromethane was not so significant as 4NPNM-EP reaction. The semi-empirical analysis on the basis of the Bell's treatment showed that the barrier width for 4NPNM-EP was larger and barrier height became much higher in comparison to the reaction of 4NPNM with the bases such as DBU or tetramethylguanidine (TMG). Those results were considered from the viewpoints of solvation effect on the transition state. | |||||
| 書誌情報 |
甲南大学紀要. 理工学編 en : Memoirs of Konan University. Science and engineering series 巻 51, 号 2, p. 141-149, 発行日 2004-12-25 |
|||||
| 出版者 | ||||||
| 出版者 | 甲南大学 | |||||
| ISSN | ||||||
| 収録物識別子タイプ | ISSN | |||||
| 収録物識別子 | 13480383 | |||||
| 書誌レコードID | ||||||
| 収録物識別子タイプ | NCID | |||||
| 収録物識別子 | AA11561231 | |||||
| 論文ID（NAID） | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | 110004688293 | |||||
| フォーマット | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | application/pdf | |||||
| 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 | |||||
