Si. Malekin et al., SYNTHESIS AND CHEMICAL-TRANSFORMATIONS OF CYLOXYMETHYL-2-OXO-2-CHLORO-1,3,2-DIOXAPHOSPHOLANE, Bioorganiceskaa himia, 23(9), 1997, pp. 747-752
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.