Difructose dianhydrides from sucrose and fructo-oligosaccharides and their use as building blocks for the preparation of amphiphiles, liquid crystals, and polymers.
Controlled selective protonic activation of the fructosyl moiety in sucrose and fructo-oligosaccharides, with pyridinium poly (hydrogen fluoride) at 20 degrees C, yielded either the kinetic product alpha-D-fructofuranose beta-D-fructofuranose 1,2':2,1'-dianhydride (1), or its thermodynamically more stable isomer alpha-D-fructofuranose beta-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-alpha-D-fructofuranose 6'-deoxy-6'-halo-beta-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.
CNRS and CEA, Département de Recherche Fondamentale sur la Matière Condensée/SESAM, Centre d'Etudes de Grenoble, France.
J M
JM
García Fernández
A
A
Gadelle
J
J
Defaye
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D003460:Crystallization; D004146:Dioxanes / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D009904:Optical Rotation; D011134:Polysaccharides / Q000138:chemical synthesis*; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013329:Structure-Activity Relationship; D013395:Sucrose
D004146:Dioxanes; D007202:Indicators and Reagents; D011134:Polysaccharides; D013141:Spiro Compounds; D013395:Sucrose