Goldwhite-Saunders

The phosphorus-containing ligand precursor H0P(0)(0 Bu)2 was originally reported in 1957 by Goldwhite and Saunders [62]. The potassium salt of the desired phosphate, K0P(0)(0 Bu)2, is used as a stable precursor to the desired acid. This salt is prepared according to the method of Zwierzak and Kluba [63] and can be stored for extended periods at room temperature. A cold (0 °C) aqueous solution of K0P(0)(0 Bu)2 is treated with concentrated HCl to form H0P(0)(0 Bu)2 as a precipitate (Eq. 1). Rapid isolation (filtration) and subsequent crystallization affords pure product in good yields (> 80%). The... 

Goldwhite, H. and Saunders, B. C. (1955) Esters containing phosphorus. Part XIII. Dialkyl phosphorobromidates. Journal of the Chemical Society, 3549-3564. 

These compounds can be prepared by the action of bromine c i a trialkyl phosphite, but a more satisfactory method recently worked out by Goldwhite and Saunders consists in treating the dialkyl hydrogen phosphite with W-bromosuccinimide. In this way dimethyl, diethyl -propyl and isopropyl phosphorobromidates have been obtained as pure liquids by distillation at very low temperature. When kept at ordinary temperatures, they gradually decompose with the evolution of the corresponding alkyl bromide. 

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