β-(1 → 4)-Polyglucuronic acids with C2/C3-ketones prepared from regenerated cellulose by catalytic oxidation using...

Three commercial regenerated cellulose samples were subjected to TEMPO-catalyzed oxidation using solid NaOCl·5H₂O as the primary oxidant for structural analyses of the oxidized products (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl). The regenerated cellulose/water slurries became transparent solutions after oxidation for 60 min. The yields of the oxidized products were almost 100 % when they were isolated as precipitates in ethanol/water mixtures. The solution-state NMR spectra revealed that the oxidized products were almost pure water-soluble β-(1 → 4)-polyglucuronic acids; the reaction conditions described herein ensured the complete oxidation of the C6-OH groups in the regenerated cellulose samples to C6-carboxy groups. However, the solid-state ¹³C NMR spectra of the oxidized products indicated that C2/C3-ketones (<20 % of the total units) were formed during side reactions, which is characteristic for oxidized products prepared from regenerated cellulose with the C2/C3-glycol structure. These ketones were likely to form intermolecular hemiacetal linkages in the oxidized products. During conductivity titration of the oxidized products, it is necessary to control the sample masses to accurately determine the carboxy contents. The mass-average degree of polymerization decreased from 330 to 890 for the original regenerated cellulose samples to 65-79 for the oxidized products; substantial depolymerization is inevitable during TEMPO-catalyzed oxidation of the regenerated cellulose samples.