Carboxymethylation is a common method used to modify the properties of cellulose and starch but, as a rule, not all of the hydroxyl groups are substituted. The products can be regarded as copolymers of unsubstituted, mono(2-, 3-, and 6-), di(2,3-, 2,6-, and 3,6-), and tri-substituted (2,3,6-) D-glucose moieties. Characterisation of the structures of the monomers in a hydrolysate of carboxymethylcellulose, using 13C-n.m.r. spectroscopy’q’and g.l.c.-(e.i.)-m.s.3, has been reported. ‘H-N.m.r. spectroscopy (90 MHz) of hydrolysates of carboxymethylcellulose has been used to determine the distribution of the carboxymethyl groups and the degree of substitution4. However, the low resolution of the ‘H-n.m.r. spectra precluded the assignment of all of the signals. A new procedure for the determination of the distribution of the substituents in carboxymethylcellulose based on the analysis of hydrolysates by high-pH anion-exchange chromatography on CarboPac PA-l with pulsed amperometric detection (h.p.a.e.c.-p.a.d.)5 allowed the isolation of all of the monomers. We now report the complete assignment of the ‘H-n.m.r. spectra of the carboxymethylated derivatives of D-glucopyranose with substituents at O-2, O-3, O-6, O-2,3, O-2,6, O-3,6, and O-2,3,6. Each of the above derivatives was an cc&mixture with various cr&ratios. Most of the resonances of the skeleton protons were assigned by combining information from 2D homonuclear Hartmann-Hahn (HOHAHA) and 1D spectra (Tables I and II). By choosing a suitable mixing time for the 2D HOHAHA spectra, the number of cross-peaks on the individual skeleton proton tracks was limited to one or two. Most of the assignments were deduced from these spectra, using additional information such as intensity differences and coupling patterns. When necessary, 2D HOHAHA spectra were recorded with longer mixing times which showed partial or complete subspectra on the H-l track of each anomer, or 2D doublequantum filtered ‘H-‘H correlation (DQF-‘H-‘H COSY) spectra were taken. The resonances of the skeleton protons that overlapped in the 2D spectra were assigned on the basis of iterative simulation and matching. The signals for the CH,COO groups appeared in a region (8 3.9-4.3) where,