Chemical synthesis of 1-O-alkyl and 1-O-acyl dihydroxyacetone-3-phosphate

Abstract

A method for the chemical synthesis of 1-O-hexadecyl dihydroxyacetone-3-phosphate is described. The synthesis was started with the preparation of O-hexadecyl glycolic acid by condensing 1-iodohexadecane with ethyl glycolate in the presence of silver oxide, followed by saponification and free acid liberation with HC1. O-Hexadecyl glycolic acid was converted to the acid chloride (with oxalyl chloride) which was condensed with diazomethane in diethyl ether to form hexadecyloxy diazoacetone. The diazoketone was decomposed by H3PO4 in dioxane to give the desired product, 1-O-hexadecyl dihydroxyacetone-3-phosphate. The product was purified by chromatography on silicic acid column followed by an acid wash. The final yield was 50% starting from O-hexadecyl glycolic acid. Analytical, spectral (IR, NMR) and chromatographic properties of 1-O-hexadecyl dihydroxyacetone-3-phosphate are described. The method described here may be used to prepare different acyl and alkyl derivatives of dihydroxyacetone phosphate in good yield as illustrated by describing the procedure for the synthesis of 1-O-palmitoyl dihydroxyacetone-3-phosphate, 1-O-hexadecyl dihydroxyacetone-3-[32P] phosphate and the dimethyl ketal of 1-O-palmitoyl [2-14C]dihydroxyacetone phosphate.