Diels-Alder Reactions of Anthracenes with Dienophiles via Photoinduced Electron Transfer

Shunichi Fukuzumi; Toshihiko Okamoto; Kei Ohkubo

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Diels-Alder Reactions of Anthracenes with Dienophiles via Photoinduced Electron Transfer

机译：蒽与亲双烯体通过光诱导电子转移的狄尔斯-阿尔德反应

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Photochemical Diels-Alder reaction of anthracene and its derivatives with dienophiles (p-benzoquinone and fumaronitrile) occurs in competition with the dimerization of anthracenes in chloroform at 298 K. The dependence of the quantum yields on the concentrations of dienophiles has revealed that the photochemical Diels-Alder reaction proceeds via electron transfer from the singlet excited states of anthracenes to dienophiles. The rates of photoinduced electron transfer are diffusion limited, agreeding with the largely negative free energy change of electron-transfer judging from the more negative one-electron oxidation potentials of the singlet excited states of anthracenes than the one-electron reduction potentials of dienophiles. The radical ion pair produced in the photoinduced Diels-Alder from the singlet excited states of anthracenes to p-benzoquinone and fumaronitrile has been detected as the transient absorption spectrum at 298 K with use of laser flash photolysis. The diradical intermediates prior to the Diels-Alder adduct formation following the photoinduced electron transfer have successfully been detected by ESR at 77 K under photoirradiation of chloroform solutions of anthracene derivatives and p-benzoquinones.

机译：蒽及其衍生物与亲二烯体（对-苯醌和富马腈）的光化学Diels-Alder反应与298 K在氯仿中蒽的二聚反应竞争。量子产率对亲二烯体浓度的依赖性表明，光化学Diels -Al醛反应通过电子从蒽的单重态激发到亲二烯体而进行。光诱导电子转移的速率受到扩散的限制，这与从蒽的单线态激发态的负电子单电子氧化势比亲二烯体的单电子还原势更为负的电子转移的负自由能变化是一致的。使用激光闪光光解法已检测到在光诱导的Diels-Alder中从蒽的单重激发态到对苯醌和富马腈产生的自由基对作为298 K的瞬态吸收光谱。在蒽衍生物和对苯醌的氯仿溶液的光辐照下，ESR在77 K下成功地检测出光诱导电子转移后Diels-Alder加合物形成之前的双自由基中间体。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2003年第28期|共7页
作者
Shunichi Fukuzumi; Toshihiko Okamoto; Kei Ohkubo;
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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
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1. Diels-Alder Reactions of Anthracenes with Dienophiles via Photoinduced Electron Transfer [J] . Shunichi Fukuzumi, Toshihiko Okamoto, Kei Ohkubo The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2003,第28期

机译：蒽与亲双烯体通过光诱导电子转移的狄尔斯-阿尔德反应
2. syn-pi-Face-and endo-selective,inverse electron-demand Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide with electron-rich dienophiles [J] . Jim Takayama, Yoshiaki Sugihara, Toshiyuki Takayanagi, Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry . 2005,第24期

机译：3,4-二叔丁基噻吩1-氧化物与富电子的亲二烯体的同π-π-表面和内向选择性，反电子需求的Diels-Alder反应
3. TRANSFER OF THE R(1)C-N(TBOC)-CR(2) UNIT FROM 2,4-DIHYDROPYRROLO[3,4-B]INDOLES TO DIENOPHILES BY DIELS-ALDER AND RETRO-DIELS-ALDER REACTIONS [J] . Sha CK., Chang CJ., Yang JF. Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry . 1996,第20期

机译：R（1）C-N（TBOC）-CR（2）单元通过DIELS-ALDER和RETRO-DIELS-ALDER反应从2,4-二氢吡咯并[3,4-B]吲哚转移至二酚
4. ONE-POT REGIOSPECIFIC SYNTHESIS OF NEW SUBSTITUTED 1,4-BENZOXAZINES THROUGH AN INVERSE ELECTRON-DEMAND HETERO DIELS-ALDER REACTION OF SIMULTANEOUSLY ELECTROGENERATED DIENE AND DIENOPHILE. [C] . MARTINE LARGERON, MARC VUILHORGNE, ESTELLE BLATTES The Meeting of the Electrochemical Society . 2001

机译：通过同时发电二烯和腙反应的逆电子杂差二胶剂反应，单壶细胞再性合成新型取代的1,4-苯并恶嗪。
5. Exploration of the inverse-electron-demand Diels-Alder (IEDDA) reaction. Rapid access to benzocoumarins via IEDDA-driven domino reactions of coumarin-fused electron-deficient dienes with electron-rich dienophiles. [D] . Pottie, Ian R. 2003

机译：逆电子需求Diels-Alder（IEDDA）反应的探索。通过IEDDA驱动的香豆素融合的电子缺陷二烯与富电子的亲二烯体的多米诺反应，可快速获得苯并香豆素。
6. Diels-Alder reactions using 47-dioxygenated indanones as dienophiles for regioselective construction of oxygenated 23-dihydrobenzfindenone skeleton [O] . Natsuno Etomi, Takuya Kumamoto, Waka Nakanishi, 2008

机译：使用47-二加氧茚满酮作为亲二烯体的Diels-Alder反应用于区域选择性构建含氧的23-二氢苯并f茚满酮骨架
7. Photoinduced intermolecular electron transfer reaction between N,N‐dimethylaniline and anthracene in acetonitrile solution: A theoretical study [O] . Koji Ando 1994

机译：乙腈溶液中N，N-二甲基苯胺和蒽之间的光突出的分子间电子转移反应：理论研究
8. Gas-Phase Intramolecular Diels-Alder Reactions of 2,3-Dimethylene-2,3-Dihydrofurans; Formation of 9-Methylanthracene and Anthracene by Pyrolysis; and Preparation of Cyclopentadienones by Flash Vacuum Pyrolysis [R] . Lee, S. K. 1987

机译：2,3-二亚甲基-2,3-二氢呋喃的气相分子内Diels-alder反应;通过热解形成9-甲基蒽和蒽;闪蒸真空热解制备环戊二烯酮

Diels-Alder Reactions of Anthracenes with Dienophiles via Photoinduced Electron Transfer

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