Difructose dianhydrides from sucrose and fructo-oligosaccharides and their use as building blocks for the preparation of amphiphiles, liquid crystals, and polymers

Article abstract of DOI:10.1016/0008-6215(94)00239-8

Controlled selective protonic activation of the fructosyl moiety in sucrose and fructo-oligosaccharides, with pyridinium poly(hydrogen fluoride) at 20°C, yielded either the kinetic product α-Dfructofuranose β-D-fructofuranose 1,2':2,1'-dianhydride (1), or its thermodynamically more stable isomer α-D-fructofuranose β-D-fructopyranose 1,2' :2,1'-dianhydride (2), depending on the hydrogen fluoride-pyridine ratio. A similar reaction was performed with 6,6'-dichloro-6,6'-dideoxysucrose, or 6,6'-dideoxy-6,6'-diiodosucrose, using a slightly higher ratio of HF resulting in the corresponding 6-deoxy-6-halo-α-D-fructofuranose 6'-deoxy-6' -halo-β-D-fructofuranose 1,2':2,1'-dianhydride derivatives. Both 6,6'-dihalides were converted, upon action of the appropriate nucleophile, into the difructofuranose dianhydride derivatives bearing the 6,6'-di-S-heptyl-6,6'-dithio, 6,6'-diazido-6,6'dideoxy and then 6,6'-diamino-6,6'-dideoxy functionalities, 6-Chloro-6-deoxy and 6-deoxy-6-iodo derivatives of 2 were also prepared by direct halogenation, and further converted into the 6-S-heptyl-6-thio, 6-azido-6-deoxy and then 6-amino-6-deoxy derivatives of 2. Reaction of chloromethyloxirane with 1 or 2 yielded hydrophilic polymers. The 6,6'-di-S-heptyl-6,6'-dithio derivative of 1 displayed liquid crystal properties. The 6,6'-dideoxy-6,6'-diiodosucrose precursor was prepared by the reaction of Garegg's iodine-imidazole-triphenylphosphine reagent with sucrose in N,N-dimethylformamide solution. Controlled selective protonic activation of the fructosyl moiety in sucrose and fructo-oligosaccharides, with pyridinium poly(hydrogen fluoride) yielded either the kinetic product α-D-fructofuranose β-D-fructofuranose 1,2′:2,1′-dianhydride (1) or its thermodynamically more stable isomer. Several derivatives were also prepared from a similar reaction with 6,6′-dichloro-6,6′-dideoxysucrose, or 6,6′-dideoxy-6,6′-diiodosucrose. Reaction of chloromethyloxirane with 1 and its isomer gave hydrophilic polymers. The 6,6′-dideoxy-6,6′-diiodosucrose precursor was prepared by the reaction of Garegg's iodine-imidazole-triphenylphosphine reagent with sucrose in N,N-dimethylformamide solution.