THE LOCATION OF THE XANTHATE GROUPS IN PARTLY SUBSTITUTED CELLULOSE XANTHATES

Abstract

Cellulose sodium xanthates of degree of substitution (D.S.) 0.4 to 0.66 were methylated to xanthate S-methyl esters which were then acetylated completely, the final xanthate D.S. remaining close to the original value. Dexanthation with aqueous chlorine dioxide near pH 4.5 and −5° removed almost all of the S-methyl xanthate groups, but the loss of a few acetyl groups from, and the retention of 1 to 2% of sulphur in, the resulting cellulose acetate could not be avoided. The original xanthate groups were presumably represented in this acetate as unsubstituted hydroxyl groups, and these were located by standard methods involving tosylation–iodination, tritylation, and oxidations with lead tetraacetate. Xanthate groups appeared to occupy the third and sixth, but not the second, position in the cellulose, and 53 to 61% of the substituent was in the sixth or primary position; one sample of viscose was "ripened" before the cellulose sodium xanthate was isolated, and the value was 81%. The results were of a preliminary nature, because severe technical difficulties reduced their reliability.