Amphiphilic Perfluoroalkylated Derivatives of Aliphatic Triols: Hemocompatibility and Effect on Perfluorocarbon Emulsion

Two sets of amphiphilic perfluoroalkylated aliphatic triols were prepared in a two-step synthesis: a protected glycerol, 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane ( 1 ) and protected 2-hydroxymethyl-2-methylpropane-1,3-diol, 5-hydroxymethyl-2,2,5-trimethyl-1,3-dioxane ( 11 ) were fluoroalkylated with racemic 2-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)- ( 2 ), or 2-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)- ( 3 ) or 2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)oxirane ( 4 ) using boron trifluoride diethyl etherate as a catalyst to afford intermediates 5 - 7 and 12 - 14 , which were deprotected by re-acetalization to the target triols HOCH 2 CH(OH)CH 2 OCH 2 CH(OH)CH 2 CF 2 (CF 2 ) n CF 3 ( n = 2, 4, 6) 8 - 10 and (OHCH 2 ) 2 C(CH 3 )CH 2 OCH 2 CH(OH)CH 2 CF 2 (CF 2 ) n CF 3 ( n = 2, 4, 6) 15 - 17 . Regioselectivity of competitive fluoroalkylation of propane-1,2-diol and butane-1,3-diol appeared to be considerably dependent on the catalyst up to 93 rel.% for the preferential fluoroalkylation at the primary hydroxy group. Hemocompatibility of the triols 8 - 10 and 15 - 17 , which was very high for linear-chain amphiphiles 9 and 10 , showed particular dependence on the starting triol and perfluoroalkyl-chain length. All amphiphiles 8 - 10 and 15 - 17 displayed very good compatibility with perfluorodecalin-Pluronic F-68 water emulsion.