Ceric-ion-initiated grafting of methyl methacrylate onto (1 → 5)-α-D-ribofuranan and (1 → 5)-α-D-xylofuranan

We report herein studies of grafting of MMA onto (1 → 5)-α-D -ribofuranan and (1 → 5)-α-D -xylofuranan by ceric ion initiation both in water and in dimethyl sulfoxide (DMSO). In aqueous medium, the graft polymer having high grafting (%) can be obtained easily without adding any nitric acid. The degradation of polysaccharide by the acidic ceric ion solution is not serious; 73–82% of its original molecular weight remained after the polymerization. In DMSO, graft polymers having lower grafting (%) and lower molecular weight of grafts were obtained.     

The Asymmteric Syntheses of Alkaloids via Electro-Oxidation of Aza-Rings

Recently, we found the N-(hydroxyalkyl) aza-rings 1 can produce 2-oxazolidine 2 through electrolysis. With the chiral side chain, the 2-oxazolidine 2 can generate a new chiral center at the 0-aminocarbon when treated with Grignard reagents. Repeat the process of electro-oxidation and substitution by Grignard reagents, we can prepare the two most popular alkaloids bases, pyrroliding and piperidine, with substitutions in an enantioselective fashion. This presentation will discuss the efficiency of electro-oxidation of aza-ring compounds in terms of the oxidation conditions, such as the applied potential, quantity of electricity, solvent effect,and temperature effect. Meanwhile, several demonstrative syntheses of chiral alkaloids, such as Monomorine,(-)-pyrroliding 197B, and(-)-Solenopsin A, will also be presented.     

A morphological analogue of japanese lacquer. Grafting of p-hydroxystyrene onto pullulan by ammonium persulfate initiation in dimethylsulfoxide

Pullulan-g-poly(p-acetoxystyrene) ( I ) was prepared using ammonium persulfate (APS) as an initiator in dimethylsulfoxide (DMSO) solution. I was deacetylated by hydrazine hydrate to yield pullulan-g-poly(p-hydroxystyrene) ( II ). The degree of polymerization of the grafted poly(p-hydroxystyrene) chain ( III ) was 15–20. Despite the effective grafting (%), this method caused the degradation of pullulan. The number of branch polymer chains per pullulan molecule were evaluated to be 0.9 to 2.5 from number average molecular weights of the permethylated II and III . The glass transition temperature of II was higher than that of III , indicating that the polar hydroxyl groups of pullulan in the graft polymer caused an increase in the rigidity of the grafted polymer chains. Pullulan-g-poly(o-hydroxystyrene) and pullulan-g-poly(MMA) were also readily prepared by this method.