Syntheses of Heptafluoro nitrosocyclo-butane and Nonafluoro nitrosocyclo-pentane and Their Reactions with Terafluoroethene, 1,3-Hexafluorobutadiene, and Tetrafluorohydrazine

摘要

Hexafluorocyclobutene and octafluorocyclopentene wre reacted with nitrosyl chloride or nitrogen dioxide in the presence of KF in acetonitrile to give 80% yields of the blue heptafluoronitrosocyclobutane (I) and nonafluoronitrosocyclopentane (II), respectively. Thermal decomposition of I and II in Pyrex glass resulted in the analogous nitro compounds CF2CF2CF2CFNO2 and CF2CF2CF2CF2CFNO2. Cycloaddition reactions of I and II with tetrafluoroethene gave the oxazetidines CF2CF2CF2CF2CFNOCF2CF2 and CF2CF2CF2CF2CFNOCF2CF2 and with 1,3-hexafluorobutadiene formed the oxazines CF2CF2CF2CFNOCF2CF-CFCF double bond and CF2CF2CF2CF2CFNOCF2CF-CFCF double bond. With jtetrafluorohydrazine in metal reaction vessels, either I and II or the cycloolefins gave difluoroamines, CF2CF2CF2CFNF2 and CF2CF2CF2CF2CFNF2. However, in the presence of Pyrex glass, N-(heptafluorocyclobutyl)-N-fluorodimide N-oxide and N-(nonafluorocyclopentyl)-N-fluorodiimide N-oxide (RfN(O)-NF double bond) resulted from heating I and II with N2F4.