Collect. Czech. Chem. Commun. 2002, 67, 1436-1448

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

Vladimír Církvaa, Robert Kapláneka, Oldřich Paletaa,* and Milan Kodíčekb

a Department of Organic Chemistry, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
b Department of Biochemistry and Microbiology, Institute of Chemical Technology, Prague, Technická 3, 166 28 Prague 6, Czech Republic


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 HOCH2CH(OH)CH2OCH2CH(OH)CH2CF2(CF2)nCF3 (n = 2, 4, 6) 8-10 and (OHCH2)2C(CH3)CH2OCH2CH(OH)CH2CF2(CF2)nCF3 (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.

Keywords: Perfluoroalkyl epoxides; Fluoroalkylations; Fluorophilic triols; Regioselectivity of fluoroalkylations; Hemocompatibility; Fluorinated surfactants; Blood substituents; Oxygen carriers.

References: 25 live references.