Fine Organic Synthesis by Anisotropic Control of Reactive Intermediates

通过反应中间体的各向异性控制进行精细有机合成

• 批准号: 10450336
• 负责人: SHIMA Kensuke
• 金额: $ 4.93万
• 依托单位: Miyazaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10450336/
• 关键词: Metalloporphyrin complex; Electron transfer; Redox-photosensitization; Photoamination; Anisotropic control; Solvent parameter; エネルギー移動; 不斉認識; βーシクロデキストリン; ポルフィリン錯体; 会合体形成

(1) We synthesized tetaraphenylporophynatoantimony complexes having second chromophore linked with methylene bridge on an axial ligands. Upon the irradiation of porphyrin ring, the fluorescence quenching of the porphyrin ring through electron tranfer. On the other hand, the irradiation of second chromophoire induced the fluorescence quenching of the second chromophore through both electron and energy tranfers.(2) In order to enhance the efficiency of the photoamination, we applied to redox-photosensiitization using 1,3,5-triphenylbenzene and 2,2'-dialkoxynaphthalene as a sensitizer to the photoamination of 1,2-diarylcyclopropanes and benzozycloheptene.(3) In order to develop the visible-light induced photodeclorination of chlorophenols, we investigated the photoreaction of the silica-gel supported teteraphenylporphynatoantimony complex in aqueous solution.(4) In order to elucidate the aymmetric recognization in the exicited state, the inclusion of the chiral benzylidene tatartrates into beta-cyclodextrin has been investigated. The behavior of the incusion were different in (+)-and (-)-isomers.(5) We have developed the solvent parameter based on the exiciplex emission of alkoxynaphthalenes linked with the p-cyanobenzoate group by methylene chain.

(1)合成了四苯基卟啉锑配合物，其轴向配体上有亚甲基桥连接的第二生色团。卟啉环在紫外光照射下，通过电子转移使卟啉环的荧光猝灭.另一方面，第二发色团的照射通过电子和能量转移引起第二发色团的荧光猝灭。(2)为了提高光胺化反应的效率，我们采用1，3，5-三苯基苯和2，2 '-二烷氧基萘作为光敏剂对1，2-二芳基环丙烷和苯并环庚烯进行了氧化还原光敏化反应。(3)为了发展可见光诱导氯酚类化合物的光脱氯反应，研究了硅胶负载四苯基卟啉锑配合物在水溶液中的光催化反应。(4)为了阐明激发态的不对称识别，研究了手性苯亚甲基酒石酸酯与β-环糊精的包结作用。在（+）-和（-）-异构体中，增敏剂的行为不同。(5)我们已经开发了基于与对氰基苯甲酸酯基团的亚甲基链连接的烷氧基萘的激基复合物发射的溶剂参数。

项目成果

M.Yasuda: "Photochemistry of Flavins in Micelles:Specific Effects of Anionic Surfactants on the Monomerization of Thymine Cyclobutane Dimers Photosensitized by Tetra-O-acyl Riboflavines" Photochem.Photobiol.67巻、2号. 192-197 (1998)

M. Yasuda：“胶束中黄素的光化学：阴离子表面活性剂对四-O-酰基核黄素光敏的胸腺嘧啶环丁烷二聚体单体化的特定影响” Photochem.Photobiol.Volume 67，第 2 期。192-197 (1998)

M.Yasuda: "Solvent Parameter based on the exciplex emission of(2-naphthoxy)polyoxalkyl p-cyanobenzoate" J.Photochem.Photobiol.A.Chem.in press. (1999)

M.Yasuda：“基于(2-萘氧基)聚氧烷基对氰基苯甲酸酯的激基复合物发射的溶剂参数”J.Photochem.Photobiol.A.Chem.in press。

M. Yamashita: "Bezophenone-Photosensitized Alkylation of Arylalkenes with Acetone, Dimethyl Sulfoxide, and Their Related Compounds in the Presence of tert-Butylamine"J. Photochem. Photobiol. A. Chem.. 118, No.3. 165-171 (1998)

M. Yamashita：“在叔丁胺存在下，芳基烯烃与丙酮、二甲基亚砜及其相关化合物的二苯甲酮光敏烷基化”J。

M. Yasuda: "Solvent Parameter based on the exciplex emission of (2-naphthoxy)polyoxalkyl p-cyanobenzoate"J. Photochem. Photobiol. A. Chemistry. 121. 149-155 (199)

M. Yasuda：“基于（2-萘氧基）聚氧烷基对氰基苯甲酸酯的激基复合物发射的溶剂参数”J。

M. Yasuda: "Photochemistry of Flavins in Micelles: Specific Effects of Anionic Surfactants on the Monomerization of thymine Cyclobutane Dimers Photosensitized by Tetra-O-acyl Riboflavines"Photochem. Photobiol.. 67巻、2号. 192-197 (1998)

M. Yasuda：“胶束中黄素的光化学：阴离子表面活性剂对四-O-酰基核黄素光敏的胸腺嘧啶环丁烷二聚体的特异性影响” Photochem.. Vol. 2. 192-197 (1998) ）