Investigations of Oxycellulose.
(p. 61) The author's results are tersely summed up in the following conclusions set forth at the end of the paper: The oxycelluloses are mixtures of cellulose and a derivative oxidised compound which contains one more atom O than cellulose (cellulose = C6H10O5), and for which the special designation Celloxin is proposed.
Celloxin may be formulated C8H6O6 or C6H10O6, of which the former is the more probable.
The various oxycelluloses may be regarded as containing one celloxin group to 1-4 cellulose groups, according to the nature of the original cellulose, and the degree of oxidation to which subjected. These groups are in chemical union.
Celloxin has not been isolated. On boiling the oxycelluloses with lime-milk it is converted into isosaccharinic and dioxybutyric acids. The insoluble residue from the treatment is cellulose.
The following oxycelluloses were investigated:
A. Product of action of nitric acid upon pine wood (Lindsey and Tollens, Ann. 267, 366).—The oxycelluloses contained
1 mol celloxin: {2 mol. cellulose on 6 hours' heating
{3 mol. cellulose on 3 hours' heating
with a ratio H: O = 1: 9 and 1: 8.7 respectively: they yielded 7 p.ct. furfural.
B. By action of bromine in presence of water and CaCO3 upon cotton.—Yield, (air-dry) 85 p.ct. Empirical composition C12H20O11 = C6H10O5.C6H10O6: yielded furfural 1.7 p.ct.
C. Cotton and nitric acid at 100°, two and a half hours (Cross and Bevan).—Yield, 70 p.ct. Composition
4 C6H10O5.C6H8O6
yielded furfural 2.3 p.ct.
D. Cotton and nitric acid at 100° (four hours).—A more highly oxidised product resulted, viz. 3 C6H10O5.C6H8O6: yielded furfural 3.2 p.ct.
By-products of oxidation.—The liquors from B were found to contain saccharic acid: the acid from C and B contained a dibasic acid which appeared to be tartaric acid.
The isolation of (1) isosaccharinic and (2) dioxybutyric acid from the products of digestion of the oxycelluloses with lime-milk at 100° was effected by the separation of their respective calcium salts, (1) by direct crystallisation, (2) by precipitation alcohol after separation of the former.