A reinvestigation of the synthesis of arsonolipids (2,3-diacyloxypropylarsonic acids).
A reinvestigation of the reactions leading to arsonolipids (2,3-diacyloxypropylarsonic acids) has been carried out in order to understand why the yields of their preparation were only moderate, although they are better than those reported for 2,3-diacyloxypropylphosphonic acid (phosphotidic acid). Thus, the reaction of glycidol and of 3-chloro-1,2-propanediol with alkaline sodium arsenite, "Na3AsO3", gives the desired product, 2,3-dihydroxypropylarsonic acid, and approximately 10% of an arsenic-containing glycerol dimer which is removed during the preparation of these arsonolipids. The step which is mainly responsible for the diminished yields is due to the reaction of the -As(SPh)2 or -AsO3H- precursor with the activated acid chlorides or carboxylic acid anhydrides to give an intermediate which cyclizes with the primary hydroxy group of the 2,3-dihydroxypropyl moiety. This cyclization does not allow the primary hydroxy group to be acylated. Such cyclization could not be avoided with RCOCl/py, (RCO)2O/DMAP, or RCOOH/DCC/DMAP acylating systems.
Tsivgoulis
Gerasimos M
GM
Department of Chemistry, University of Patras, Patras, Greece. tsivgoulis@chemistry.upatras.gr
Ioannou
Panayiotis V
PV
D000215:Acylation; D001152:Arsenicals / Q000138:chemical synthesis* / Q000737:chemistry*; D018053:Arsenites / Q000737:chemistry; D001667:Binding, Competitive; D002264:Carboxylic Acids / Q000737:chemistry; D002627:Chemistry, Physical / Q000379:methods; D002855:Chromatography, Thin Layer / Q000379:methods; D019281:Dimerization; D005990:Glycerol / Q000737:chemistry; D008055:Lipids / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D015394:Molecular Structure; D017670:Sodium Compounds / Q000737:chemistry
D001152:Arsenicals; D018053:Arsenites; D002264:Carboxylic Acids; D008055:Lipids; D017670:Sodium Compounds; C017947:sodium arsenite; C054806:arsonic acid; D005990:Glycerol