Researches on Cellulose, 1895-1900Cross, C. F. (Charles Frederick)
Science
Researches on Cellulose, 1895-1900
Cross, C. F. (Charles Frederick)
Cellulose
The experimental numbers require correcting for the amount of loss in
the form of products soluble in the acid mixture, viz. 7.6 p.ct.; but
they remain within the range of the experimental errors sufficiently to
show that the benzoyl group limits the number of OH groups taking part
in the ester reaction to three. The corrected yield per 1 mol. of jute
benzoate (410) is 576, as against the calculated 590 for 4HNO_{3}
reacting. A loss of 1H_{2}O per molecule by internal condensation is
therefore indicated.
~Denitration.~--The removal of the nitric groups from the esters is
effected by digestion with ammonium sulphide. But the reactions are by
no means simple. There is considerable hydrolysis of the lignocellulose
to soluble products. Thus the _tetranitrate_ yields only 46.4 of
denitrated fibre in place of the calculated 66. The product is a
cellulose, yielding only 0.5 per cent. furfural. The hydrolysed
by-products, moreover, when freed from sulphur and distilled from
hydrochloric acid, yielded only an additional 2.5 p.ct. furfural,
calculated to the original lignocellulose.
These statistics confirm the evidence that the ester reaction is not
simple. Such changes take place in the lignone-beta-cellulose complex
that they revert, not to their original form, but to soluble derivatives
of different constitution. The mixed nitrate from the benzoate is
denitrated to a cellulose amidobenzoate, which confirms the localisation
of a nitro-group in the benzoyl residue.
(p. 157) ~General Characteristics of the Lignocelluloses.~--Later
investigations have somewhat modified and simplified our views of the
constitution of the typical lignocellulose (jute), so far as this can be
dealt with by the statistics of its more important decompositions
(original, pp. 157-161).
~Cellulose.~--There is little doubt that the furfural-yielding groups of
the original are isolated in the form of the beta-cellulose. Tollens
emphasises this fact in his studies of cellulose-estimation methods. We
had previously shown (original, p. 159) that the yield of furfural is
not affected by the _chlorination_, but it appears from our numbers that
only 50 p.ct. of these groups remain in the isolated cellulose, the
residue undergoing hydrolysis to soluble compounds. In a carefully
regulated hydrolysis following the chlorination it appears that the
furfuroids are almost entirely conserved in the form of a cellulose.
Moreover, an investigation of the products dissolved by sodium sulphite
solution from the chlorinated fibre has shown that they are practically
free from furfuroids. This enables us to exclude the furfural-yielding
groups from the lignone complex. At the same time, through our later
studies of the hydroxyfurfurals, it is certain that these products are
represented in the fibre substance and probably in the lignone complex.
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