Part 8 (1/2)

The hydralcellulose boiled with Fehling's solution reduced 1/12 of the amount required for an equal weight of glucose.

Digested with caustic soda solution it yielded 33 p.ct. of its weight of the soluble 'acid cellulose.' This product was purified and a.n.a.lysed with the following result: C 43.35 H 6.5. For the direct production of the 'acid' derivative, cellulose was boiled with successive quant.i.ties of 30 p.ct. NaOH until _dissolved_. It required eight treatments of one hour's duration. On adding sulphuric acid to the solutions the product was precipitated. Yield 40 p.ct. a.n.a.lyses:

C 43.8 43.8 43.7 H 6.2 6.2 6.3

The cellulose reprecipitated from solution in Schweizer's reagent gave similar a.n.a.lytical results:

C 43.9 43.8 44.0 H 6.5 6.3 6.4

_Conversion into nitrates._--The original cellulose, hydral- and acid cellulose were each treated with 10 times their weight of HNO_{3} of 1.48 sp.gr. and heated at 85 until the solution lost its initial viscosity.

The products were precipitated by water and purified by solution in acetone from which two fractions were recovered, the one being relatively insoluble in ethyl alcohol. The various nitrates from the several original products proved to be of almost identical composition,

C 32.0 H 4.2 N 8.8

with a molecular weight approximately 1350. The conclusion is that these products are all derivatives of a 'hydralcellulose'

6C_{6}H_{10}O_{5}H_{2}O.

FORMATION OF FURFURALDEHYDE FROM CELLULOSE, OXYCELLULOSE, AND HYDROCELLULOSE.

By LEO VIGNON (Compt. rend., 1898, 126, 1355-1358).

(p. 54) Hydrocellulose, oxycellulose, and 'reduced' cellulose, the last named being apparently identical with hydrocellulose, were obtained by heating carefully purified cotton wool (10 grams) in water (1,000 c.c.), with (1) 65 c.c. of hydrochloric acid (1.2 sp.gr.), (2) 65 c.c. of hydrochloric acid and 80 grams of pota.s.sium chlorate, (3) 65 c.c. of hydrochloric acid and 50 grams of stannous chloride. From these and some other substances, the following percentage yields of furfuraldehyde were obtained: Hydrocellulose, 0.854; oxycellulose, 2.113; reduced cellulose, 0.860; starch, 0.800; bleached cotton, 1.800; oxycellulose, prepared by means of chromic acid, 3.500. Two specimens of oxycellulose were prepared by treating cotton wool with hydrochloric acid and pota.s.sium chlorate (A), and with sulphuric acid and pota.s.sium dichromate (B), and 25 grams of each product digested with aqueous potash. Of the product A, 16.20 grams were insoluble in potash, 2.45 grams were precipitated on neutralisation of the alkaline solution, and 6.35 grams remained in solution, whilst B yielded 11.16 grams of insoluble matter, 1.42 grams were precipitated by acid, and 12.42 grams remained in solution. The percentage yields of furfuraldehyde obtained from these fractions were as follows: A, insoluble, 0.86; precipitated, 4.35; dissolved, 1.10. B, insoluble, 0.76; precipitated, 5.11; dissolved, 1.54. It appears, from the foregoing results, that the cellulose molecule, after oxidation, is easily decomposed by potash, the insoluble and larger portion having all the characters of the original cellulose, whilst the soluble portion is of an aldehydic nature, and contains a substance, precipitable by acids, which yields a relatively large amount of furfuraldehyde.

UNTERSUCHUNGEN uBER DIE OXYCELLULOSE.

O. V. FABER und B. TOLLENS (Berl. Ber., 1899, 2589).

~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 = C_{6}H_{10}O_{5}), and for which the special designation _Celloxin_ is proposed.

Celloxin may be formulated C_{8}H_{6}O_{6} or C_{6}H_{10}O_{6}, 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_ CaCO_{3} _upon cotton_.--Yield, (air-dry) 85 p.ct. Empirical composition C_{12}H_{20}O_{11} = C_{6}H_{10}O_{5}.C_{6}H_{10}O_{6}: yielded furfural 1.7 p.ct.