Dinitrogen pentoxide alkenes, reactions with

Alkenes react with dinitrogen pentoxide in chlorinated solvents to give a mixture of /3-nitro-nitrate, vic-dinitro, vic-dinitrate ester and nitroalkene compounds. At temperatures between -30 °C and -10 °C the /3-nitro-nitrate is often the main product. The /3-nitro-nitrates are inherently unstable and readily form the corresponding nitroalkenes." Propylene reacts with dinitrogen pentoxide in methylene chloride between -10 °C and 0°C to form a mixture of l-nitro-2-propanol nitrate (27 %) and isomeric nitropropenes (12 %). The same reaction with cyclohexene is more complicated." ... 

The use of oxetanes for the synthesis of polynitrate esters is generally of less value than the use of epoxides, which are readily available from the epoxidation of alkenes. The analogous reaction of azetidines with dinitrogen pentoxide is a route to 1,3-nitramine-nitrates and these reactions are discussed in Section 5.8.2. ... 

Canfield and Rohrback ° reported on the reaction of some electron-deficient difluo-roaminoalkenes with dinitrogen pentoxide in chloroform at subambient temperatures. Contrary to previous work that the /3-nitro-nitrate ester should be the main product, the corresponding vtc-dinitrate esters were isolated from these reactions l,4-bis(iV,iV-difiuoroamino)-2,3-butanediol dinitrate (55), 3,4-bis(iV,iV-difluoroamino)-l,2-butanediol dinitrate (56) and 3-(iV,iV-difluoroamino)-1,2-propanediol dinitrate (57) were isolated in 30 %, 27 %, and 55 % yields respectively, from the parent alkenes. 

Typical procedure The mole ratio of alkene t-BuOOH catalyst was 10 10 0.25 and 40 mmol of the olefin serving as its own solvent. Thus, 10 mmol of TBHP (80% in di-tert-butyl peroxide) and 0.25 mmol of vanadium pentoxide were added to 50 mmol of the olefin and the reaction mixture was stirred at 60°C under a dinitrogen atmosphere. The products formed were analyzed by GC by comparison of their retention time with those of authentic samples. Good yields of epoxides were obtained only with an excess of olefin to TBHP of 5 1. That the olefin doubles up as the solvent makes for a more practical procedure. Typical results (34) are shown in Table 1 ... 

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