Researches on Cellulose, 1895-1900Cross, C. F. (Charles Frederick)
Science
Researches on Cellulose, 1895-1900
Cross, C. F. (Charles Frederick)
Cellulose
As there has been no addition of experimental facts directly
contributing to the solution of the problem, the material available for
a discussion of the probabilities remains very much as stated in the
first edition, pp. 75-77. It is now generally admitted that the
tetracetate _n_ [C_{6}H_{6}O.(OAc)_{4}] is a normal cellulose ester;
therefore that four of the five O atoms are hydroxylic. The fifth is
undoubtedly carbonyl oxygen. The reactions of cellulose certainly
indicate that the CO- group is ketonic rather than aldehydic. Even when
attacked by strong sulphuric acid the resolution proceeds some
considerable way before products are obtained reducing Fehling's
solution. This is not easily reconcilable with any polyaldose formula.
Nor is the resistance of cellulose to very severe alkaline treatments.
The probability may be noted here that under the action of the alkaline
hydrates there occurs a change of configuration. Lobry de Bruyn's
researches on the change of position of the typical CO- group of the
simple hexoses, in presence of alkalis, point very definitely in this
direction. It is probable that in the formation of alkali cellulose
there is a constitutional change of the cellulose, which may in effect
be due to a migration of a CO- position within the unit group. Again
also we have the interesting fact that structural changes accompany the
chemical reaction. It is surprising that there should have been no
investigation of these changes of external form and structure, otherwise
than as mass effects. We cannot, therefore, say what may be the
molecular interpretation of these effects. It has not yet been
determined whether there are any intrinsic volume changes in the
cellulose substance itself: and as regards what changes are determined
in the reacting unit or molecule, we can only note a fruitful subject
for future investigation. _A priori_ our views of the probable changes
depend upon the assumed constitution of the unit group. If of the
ordinary carbohydrate type, formulated with an open chain, there is
little to surmise beyond the change of position of a CO- group. But
alternative formulae have been proposed. Thus the tetracetate is a
derivative to be reckoned with in the problem. It is formed under
conditions which preclude constitutional changes within the unit groups.
The temperature of the main reaction is 30 deg.-40 deg., the reagents are used
but little in excess of the quantitative proportions, and the yields are
approximately quantitative. If now the derivative is formed entirely
without the hydrolysis the empirical formula C_{6}H_{6}O.(OAc)_{4}
justifies a closed-ring formula for the original viz.
CO<[CHOH]_{4}>CH_{2}; and the preference for this formula depends upon
the explanation it affords of the aggregation of the groups by way of
CO-CH_{2} synthesis.
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