Synthetic Application of Photochemical Electron Transfer in Solvents with Relatively Low Polarity.

(1)研究了在1，2-二甲氧基乙烷、四氢呋喃和1，4-二氧六环等极性较低的溶剂中，对二氰苯存在下，菲与丙胺的光胺化反应。在Et_4NbF_4存在下发生光胺化反应生成9-丙氨基-9，10-二氢菲，而在无盐条件下不发生光胺化反应。我们推测光胺化的机理是通过盐诱导的电荷将菲和对二氰基苯之间的激基化合物分离成离子自由基，以及在盐的存在下，萘、2，3-二甲基萘和菲的光胺化反应得到胺化产物。(2)阐述了菲类化合物光胺化的立体化学。结果表明，胺和氨主要以反式方式加成芳烃。胺化反应的立体选择性不依赖于溶剂的极性。(3)在三乙胺存在下，2，2-二芳基氧杂环己烷在正己烷中发生光化学Rg裂解反应，选择性地生成1，1-二芳基乙烯。光反应可能通过氧杂环己烷和三乙胺之间的激基络合物进行。

(1) The photoamination of phenanthrene with propylamine in the presence of p-dicyanobenzene was investigated in solvents with relatively low polarity such as 1, 2-dimethoxyethane, tetrahydrofuran, and 1, 4-dioxane. The photoamination in the presence of Et_4NBF_4 occurred to give 9-proplyamino-9, 10-dihydrophenanthrene, while photoamination in the absence of the salt did not occur al all. We assume the mechanism for the photoamination via salt-induced charge separation of the exciplexes between phenanthrene and p-dicyanobenzene into ion radicals.Also, the photoamination of naphthalenes, 2, 3-dimethylnaphthalene, and anthracene proceeded in the presence of the salt to give aminated products.(2) The stereochemistry of the photoamination was elucidated for phenanthrene derivatives. It is found that the amine and ammonia add to the arenes in the trans manner predominantly. The stereoselectivities of amination did not depend on solvent polarity.(3) Photochemical rig-cleavage reaction of 2, 2-diaryloxetanes in the presence of triethylamine proceeded in hexane to give 1, 1-diarylethenes selectively. The photoreaction was suggested to occur via exciplex between the oxetane and triethylamine.