Fine Organic Synthesis by Anisotropic Control of Reactive Intermediates

(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。

(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.