Synthesis and Acid Hydrolysis of Monophosphate and Pyrophosphate Esters of Phytanol and Phytol

Abstract

Monophytanyl phosphate was synthesized by phosphorylation of phytanol with diphenylphosphoryl monochloride followed by catalytic hydrogenolysis of the phenyl groups; the product was isolated as the dipotassium salt. The phytanyl pyrophosphate was prepared by phosphorylation of phytanol with monophenylphosphoryl dichloride followed by aminolysis and saponification of the resulting phytanylmonophenylphosphoryl monochloride to the phytanyl phosphoramidate. The latter, as the cyclohexylamine salt, was reacted with dioxane diphosphate in the presence of pyridine to give the desired phytanyl pyrophosphate isolated as the tripotassium salt. Alternatively, the phytanyl pyrophosphate was made from phytanyl monophosphate via the phosphomorpholidate. The 2-phytenyl (phytyl) pyrophosphate was synthesized more directly by phosphorylation of phytol with di-(triethylammonium) phosphate in the presence of trichloroacetonitrile in acetonitrile as solvent. The phytyl pyrophosphate and the accompanying phytyl monophosphate were isolated as tri- and diammonium salts, respectively. These mono- and pyrophosphates were characterized by elementary analysis, infrared spectra, and behavior towards acid hydrolysis; the hydrolysis products formed are characteristic of the phytyl or phytanyl phosphate hydrolyzed and may be used for their identification.