Diphenyl chlorophosphate, hydrolysis

DHAP has also been prepared by phosphorylation of dihydroxyacetone with glycerol kinase in the presence of ATP, with in situ regeneration of ATP, giving yields in excess of 80%. The use of chemical methods260 c for the preparation of DHAP generates a pure product, which results in a cleaner aldol reaction. In an improved and commonly used chemical preparation, the protected dimer of dihydroxyacetone was phosphorylated with diphenyl chlorophosphate, followed by hydrogenolysis and hydrolysis, to give clean DHAP in 61% yield (Scheme 5.8).28... 

Several alternative procedures have been developed for chemical synthesis of 41. Acetals of the dimer of 47 can be phosphoryated using phosphoroxy chloride [184] or diphenyl chlorophosphate [185], or by phosphitylation then oxidation [186]. After phosphate deprotection, free 41 is obtained, by acid hydrolysis, in overall yields of up to 60%. New procedures have recently been developed by controlled successive substitutions of dibromoacetone [187, 188] or by controlled hydrolysis of a cyclic phosphate diester of 47 [189]. 

Phosphonation of poly(aryloxyphosphazenes) via lithiophenoxy intermediates was realized via addition of tert-butyllithium to a solution of the polymer in THF at -75 °C. The lithiated polymers were then treated with diphenyl chlorophosphate, and subsequent basic hydrolysis and acidification yielded phenylphosphonic groups, as shown in Scheme 26. 

Kinetic studies of the aminolysis of bis(Y-phenyl) chlorophosphates ([YCgH40]2 (P=0)C1 Y = H, 4-Me, 4-MeO, 3-MeO) by anilines and deuterated anilines showed that the reaction proceeded via a stepwise mechanism, with rate-determining breakdown of the trigonal bipyramidal intermediate. The effects of solvents and solvent mixtures upon the rates of hydrolysis of diphenyl and bis-(2,4-dichlorophenyl) chlorophosphate showed that there were large sensitivities towards changes in solvent nucleophilicity, consistent with an 5 ivf2(P) process. ... 

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