Synthesis of amphiphilic phenylazophenyl glycosides and a study of their liquid crystal properties.
Several 4-(4'-N,N-didodecylaminophenylazo)phenyl 1,2-trans glycosides 5a-e with various carbohydrate heads (beta-D-gluco, beta-D-galacto, beta-lacto, beta-D-xylo, and alpha-D-manno) have been synthesized. The key step was the formation of phenyldiazonium tetrafluoroborates 2a-e from the per-O-acetylated 4-aminophenyl glycosides 1a-e. These salts were condensed with N,N-didodecylaniline under phase transfer conditions and the per-O-acetylated 4-(4'-N,N-didodecylaminophenylazo)phenyl 1,2-trans glycosides 4a-e were fully de-O-acetylated by the Zemplén method. The self-organizing liquid crystal properties of the compounds were investigated by a variety of techniques, including polarized light microscopy, differential scanning calorimetry, and X-ray diffraction. All but one of the materials exhibited smectic A, lamellar phases. Remarkably, the glucose derivative exhibited a rectangular disordered columnar phase. This result has implications with respect to the induced curvature created by the recognition processes of the glucose headgroup relative to the other sugar moieties and to the prevalence of various glycolipids in cell membranes
Laurent
Nicolas
N
Laboratoire de Chimie Organique II, Unité Mixte de Recherche CNRS 5181, Université Lyon 1, Chimie Physique Electronique de Lyon, 43 Bd du 11 Novembre 1918, F 69622 Villeurbanne, France.
Lafont
Dominique
D
Dumoulin
Fabienne
F
Boullanger
Paul
P
Mackenzie
Grahame
G
Kouwer
Paul H J
PH
Goodby
John W
JW
D001391:Azo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002241:Carbohydrates / Q000138:chemical synthesis* / Q000737:chemistry; D003460:Crystallization; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D014961:X-Ray Diffraction
D001391:Azo Compounds; D002241:Carbohydrates; D006027:Glycosides