Some Chemistry of 2,8-Dioxa-5-Aza-1-Phosphabicyclo[3.3.0] Octane and 2,10-Dioxa-6-Aza-1-Phosphabicyclo[4.4.0] Decane. Further Evidence for the Biphilic Insertion Mechanism

2,8-Dioxa-5-aza-1-phosphabicyclo[3.3.0] octane, 1, and 2,10-dioxa-6-aza-1-phosphabicyclo[4.4.0] decane, 2, both react with diethyl peroxide to give phosphoranes containing two ethoxy groups. The reactivities of 1 and 2 towards diethyl peroxide are very different. The reaction of 1 at 0°C in methylene chloride is complete after 7 days whereas 2 and diethyl peroxide in methylene chloride require 30 days at room temperature for 89% reaction. The opposite reactivity of 1 and 2 are found in their reactions with diphenyl disulfide. These data strongly support a direct insertion by phosphorus into the oxygen-oxygen bond of the peroxide. Compounds, 1 and 2 were allowed to react with trifluoroethoxy benzenesulfenate and 1,1,1,3,3,3-hexafluoroisopropoxy benzenesulfenate. Dioxyphosphoranes were formed in all cases. The structures of these materials are discussed. Products of condensation reactions of 1 and 2 were also obtained and structural features are noted.