- Clean nitrations: Novel syntheses of nitramines and nitrate esters by nitrodesilylation reactions using dinitrogen pentoxide (N2O5)
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In this novel nitration method dinitrogen pentoxide (N2O5) in an inert solvent is used as the nitrating agent, thereby removing the need for strong acids as the reaction medium. The N2O5 cleaves heteroatom-silicon bonds, in silylamines and silyl ethers respectively, to yield the desired energetic groupings (nitramines or nitrate esters respectively) without liberation of acids which would occur with conventional substrates (amines or alcohols). These nitrodesilylation reactions proceed cleanly and in good yield, and the scope of the reaction is illustrated by 29 examples, some of which produce high energy compounds, notably plasticisers and an energetic polymer precursor. These reactions are therefore potentially clean nitrations for the manufacture of energetic compounds which will minimise the impact of this activity on the environment in the future.
- Millar, Ross W.,Philbin, Simon P.
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p. 4371 - 4386
(2007/10/03)
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- Preparation of Di- and polynitrates by ring-opening nitration of epoxides by dinitrogen pentoxide (N2O5)
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Eighteen epoxides of various kinds were reacted with N2O5 in chlorinated hydrocarbon solvents (principally CH2Cl2) to give vicinal nitrate ester products by a novel ring-opening nitration reaction. The procedure offers easier temperature control and simpler isolation procedures compared with conventional mixed acid nitrations; it also enables selective nitration reactions to be carried out on polyfunctional substrates. The scope and limitations of the reaction, as well as those of an alternative route utilising N2O4 with in situ oxidation of an intermediate nitrite-nitrate, are discussed.
- Golding, Peter,Millar, Ross W.,Paul, Norman C.,Richards, David H.
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p. 7037 - 7050
(2007/10/02)
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