Alcohols Atherton-Todd phosphorylation

Atherton-Todd phosphorylation of alcohols and phenols (Table 3.22)... 

Phosphorylation of primary alcohols and phenols. Zwierzak has found that the Atherton-Todd phosphorylation can be carried out advantageously under phase-transfer eatalysis. Carbon tetrachloride and 50% aqueous sodium hydroxide serve as the solvent pair tetra-/i-butylammonium bromide or benzyltriethyl-ammonium chloride serve equally well as catalysts. Yields are 35 90% for primary alcohols and phenols low yields are obtained from other alcohols. 

The catalysed two-phase adaptation of the Atherton-Todd procedure is effective for the phosphorylation of primary alcohols and of phenols [6] to produce trialkyl phosphates and dialkyl aryl phosphates. Trialkyl phosphates have also be obtained in high yield (>75%) from the alkylation of preformed tctra-n-butylammonium di-/-butylphosphate [7], Subsequent cleavage of the /-butyl groups provide a simple synthesis of monoalkyl phosphates. 

PTC has been used efficiently for chlorination of dialkylphosphite and subsequent phosphorylation of secondary amines, O-alkylhydroxylamines, alcohols, etc. (Atherton-Todd reaction) via halophilic reaction with carbon tetrachloride ... 

The Atherton-Todd reaction is used to introduce a phosphoryl group in amines, but this procedure encounters difficulties when applied to alcohols. Sonication extended its scope to this last type of substrate (Eq. 26). 

Atherton, F.R. and Todd, A.R., Phosphorylation. M. Reactions of phosphites with polyhalogen compounds in the presence of bases and its application to the phosphorylation of alcohols,. Chem. Soc., 674, 1947. 

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