Metathesis between alkyl halides and silver nitrate

1 Metathesis between alkyl halides and silver nitrate 

The reaction of alkyl halides with silver nitrate constitutes an extremely useful method for the synthesis of high purity nitrate esters on a laboratory scale. ° The driving force for these reactions is the formation of the insoluble silver halide. Reactions have been conducted under homogenous and heterogeneous conditions. For the latter a solution of the alkyl halide in an inert solvent like benzene or ether is stirred with finely powdered silver nitrate. However, this method has been outdated and reactions are now commonly conducted under homogeneous conditions using acetonitrile as solvent. 

The scope of these reactions is illustrated by the variety of functionalized nitrate esters which can be prepared (Table 3.1). In general, primary and secondary alkyl iodides and bromides 

Synthesis of nitrate esters from the reaction of alkyl halides with silver nitrate 

Tojo and co-workers reported a one-pot synthesis of alkyl nitrates from alcohols via the alkyl iodide the alcohol is treated with a mixture of iodine, triphenylphosphine and imidazole in diethyl ether-acetonitrile, and the resulting alkyl iodide is reacted in situ with silver nitrate (Equation 3.8). Reported yields for primary alcohols are good to excellent but yields are lower for secondary alcohols. 

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