2- (ペルフルオロオクチル) エタノール=ジシクロペンタジエン付加物の合成とその酸素酸化初期生成物

抄録

8- or 9- [2- (perfluorooctyl) ethoxy] -tricyclo [5. 2. 1.0^{2' 6}] deca- 3- en (1) was synthesized by the reaction of 2- (perfluorooctyl) ethanol with dicyclopentadiene in the presence of boron trifluo-ride- ethyl ether complex. The reaction rate exceeded that of the linear hydrocarbon alcohol with dicyclopentadiene. At the start of liquid phase oxygen oxidation, radicals were formed by the abstraction of hydrogen at the allyl position of (1) in the presence of azobis (isobutyronitrile), and peroxy radicals were subsequently produced by oxygen attack. The peroxy radical produced hydroperoxide by hydrogen abstraction in an intermolecular manner. At above a concentration of 10 % hydroperoxide, was converted to the corresponding hydroxide and ketone. The activation energy of hydroperoxide formation in neat was 20.6 kcal mol^-1. Neither the addition of the peroxy radical to a double bond nor its coupling could be detected.