Benzoolysis of diacylglycerophosphocholines: dephosphorylation and sequential formation of isomeric reaction products.
Benzoolysis experiments are reported in which diacylglycerophosphocholine is heated at 100 degrees C with benzoic anhydride for variable periods of time. It is shown that more than 90% of the phospholipid is dephosphorylated after 5 h of heating. Lipid extracts of the reaction mixture contained 1,2- and 1,3-diacylglycerobenzoate and 1,2- and 1,3-diacylglycerol in nearly constant isomer ratios of about 3:1 and 1:2, respectively, independent of the heating and extraction time. The total amount of isomeric diacylglycerobenzoates increased more slowly with increasing heating time that corresponded with the dephosphorylation rate, complete benzoylation being attained only after a 15 h heating period. The total amount of isomeric diacylglycerols went through a maximum after about 4 h and vanished after 15 h of heating. Addition of 4-dimethylaminopyridine subsequent to the heating period resulted in rapid and complete benzoylation of dephosphorylated phospholipid. However, the ratio of 1,2- to 1,3-diacylglycerobenzoate then found in the lipid extract depended on heating time, changing from less than 1:1 to about 3:1 upon an increase of heating time from 1 to 15 h. The results are interpreted in terms of two consecutive reactions. In a relatively fast first step, a dephosphorylated intermediate is formed, which in the molten benzoic anhydride, is slowly benzoylated. The intermediate yields diacylglycerols upon extraction in the absence of 4-dimethylaminopyridine and diacylglycerobenzoates upon extraction in the presence of 4-dimethylaminopyridine.
Gelsema
W J
WJ
Department of Analytical Chemistry, Utrecht University, The Netherlands.
van den Brink
O F
OF
van den Bosch
H
H
D001565:Benzoates; D002250:Carbon Radioisotopes; D002851:Chromatography, High Pressure Liquid; D004075:Diglycerides / Q000737:chemistry*; D006358:Hot Temperature; D007202:Indicators and Reagents; D007536:Isomerism; D010713:Phosphatidylcholines / Q000737:chemistry*; D012588:Scintillation Counting; D013329:Structure-Activity Relationship
D001565:Benzoates; D002250:Carbon Radioisotopes; D004075:Diglycerides; D007202:Indicators and Reagents; D010713:Phosphatidylcholines; C044295:1,2-dioctanoylglycerol; C102988:benzoic anhydride