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

(1)在1,2 -二甲氧基乙烷、四氢呋喃、1,4 -二恶烷等极性较低的溶剂中，研究了对二苯甲酸存在下，菲与丙胺的光胺化反应。在有Et_4NBF_4存在的情况下，产生了9- proplyamo - 9,10 -二氢菲，而在没有盐的情况下，则完全没有发生光氨化反应。我们假设光胺化的机制是通过盐诱导菲和对二苯甲酸之间的络合物的电荷分离成离子自由基。此外，萘、2,3 -二甲基萘和蒽在盐的存在下进行光胺化反应，得到胺化产物。(2)阐明了菲衍生物光胺化反应的立体化学性质。发现胺和氨主要以反式方式加入芳烃。胺化反应的立体选择性与溶剂极性无关。(3)在三乙胺存在下，2,2 -二乙基氧乙烷在己烷中进行光化学裂解反应，选择性地得到1,1 -二乙基乙烯。光反应是通过氧乙烷和三乙胺之间的激合发生的。

(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.