SYNTHESIS AND CHEMICAL-TRANSFORMATIONS OF CYLOXYMETHYL-2-OXO-2-CHLORO-1,3,2-DIOXAPHOSPHOLANE

Cyclophosphorylation of 1-hexadecylglycerol with phosphorus oxychlorid e afforded 4-hexadecyloxymethyl-2-oxo-2-chloro-1,3 2-dioxaphospholane (I) with high yield. By means of H-1, C-13, and P-31 NMR, this was sho wn to be a 1:9 mixture of two stable epimers with equatorial and axial configuration of the chlorine atom, respectively. Phospholane (I) ent ered into nucleophilic reactions with KHCO3 and HN(Pr-i)(2) to give 80 -85% yields of the chlorine substitution products with the phospholane cycle remaining intact. Interaction of the phospholane (I) with water or choline tosylate also initially produced substituted phospholanes, as shown by NMR. Subsequent hydrolysis led to the cleavage of the pho spholane ring and to formation of isomeric 1-hexadecylglycero-2- and 3 -phosphates and 1-hexadecylglycero-2- and 3-phosphocholines, respectiv ely. A method for the separation of isomeric phosphates was developed, which made it possible to isolate 1-hexadecylglycero-2-phosphate and 1-hexadecylglycero-3-phosphate.