682. Studies on phosphorylation. Part XIV. The solvolysis by phenols of benzyl phosphates

Mechanisms of Nucleophilic Substitution in Phosphate Esters

“…Full publication of the experimental facts of the matter has not been made. Under neutral or acidic conditions, alcohols attack triesters of phosphoric acid with primary alcohols chiefly at carbon, rather than at phosphorus (153,189,226). Although trimethyl phosphate may thus be used as a methylating reagent in a manner similar to the use of dimethyl sulfate, it appears to be less reactive than the sulfate ester and serves no unique synthetic purpose.…”

Novelties of solid-liquid phase transfer catalyzed synthesis of benzyl diethyl phosphate from the sodium salt of diethyl phosphate

“…To adequately utilize the side-product of industrial products sodium salt of diethyl phosphate, the effect of molar ratios of sodium salt of diethyl phosphate to benzyl chloride were studied for 1:1, 1:1.2, 1:1.5, and 1:2 under otherwise similar conditions (entries 4, 10-12). The yield of the product was not obviously enhanced with the use of higher concentration of the TBAB catalyst (up to 8 mol%, based on the sodium salt of diethyl phosphate, entries 4-9) and a 1.2~2.0 times excess benzyl chloride (entries [10][11][12], due to the fact that the concentration of (EtO)2P(O)O -Q + extracted into the ω-phase retains almost constant with the ion-exchange reaction proceeding. This phenomenon is also observed in most other solid-liquid phase transfer catalyzed reactions [21,22].…”

“…Recently, the cross-coupling reaction of substituted benzyl diethyl phosphates with arylboronic acids and arylmagnesium reagents has been explored by McLaughlin [10] and Kofink et al [11], respectively. The generally reported method for the preparation of a series of substituted benzyl diethyl phosphates was the corresponding substituted benzyl alcohols by phosphorylation with diethyl chloro-phosphate in the presence of triethylamine or pyridine, and the yields were low [12][13][14]. Clearly, there is a need for improving synthesis of substituted benzyl diethyl phosphates.…”

The Synthesis of Nucleotide Coenzymes

“…Complete removal of benzyl groups can also be achieved by solvolysis in phenol, 0-and p-benzylphenols being formed simultaneously (45). This has been carefully studied, and complete removal of benzyl groups occurs in dioxane or ethanol solution using platinum, palladium, or nickel catalysts (6).…”