Researches on Cellulose, 1895-1900Cross, C. F. (Charles Frederick)
Science
Researches on Cellulose, 1895-1900
Cross, C. F. (Charles Frederick)
Cellulose
In analysing these products we have employed the Dumas method for _total
nitrogen_. For the O.NO_{2} groups we have found the nitrometer and the
Schloesing methods to give concordant results. For the NO_{2} groups it
was thought that Limpricht's method, based upon reduction with stannous
chloride in acid solution (HCl), would be available. The quantitative
results, however, were only approximate, owing to the difficulty of
confining the reduction to the NO_{2} groups of the nitrobenzoyl
residue. By reduction with ammonium sulphide the O.NO_{2} groups were
entirely removed as in the case of the cellulose nitrates; the NO_{2}
was reduced to NH_{2} and there resulted a cellulose amidobenzoate,
which was diazotised and combined with amines and phenols to form yellow
and red colouring matters, the reacting residue remaining more or less
firmly combined with the cellulose.
_Cellulose dinitrate-dinitrobenzoate, and cellulose
trinitrate-dinitrobenzoate._--On treating the fibrous benzoate--which is
a dibenzoate on the C_{12} basis--with the acid mixture under the usual
conditions, a yellowish product is obtained, with a yield of 140-142
p.ct. The nitrobenzoate is insoluble in ether alcohol, but is soluble in
acetone, acetic acid, and nitrobenzene. In purifying the product the
former solvent is used to remove any cellulose nitrates. To obtain the
maximum combination with nitroxy-groups, the product was dissolved in
concentrated nitric acid, and the solution poured into sulphuric acid.
The following analytical results were obtained (a) for the product
obtained directly from the fibrous benzoate and purified as indicated,
(b) for the product from the further treatment of (a) as described:
Found Calc. for
(a) (b) Dinitrate Trinitrate
dinitrobenzoate dinitrobenzoate
Total Nitrogen 7.84 8.97 7.99 9.24
O.NO_{2} " 5.00 5.45 4.00 5.54
NO_{2} (Aromatic) 2.84 3.52 3.99 3.70
With the two benzoyl groups converted into nitro-benzoyl in each
product, the limit of the ester reaction with the cellulose residue is
reached at the third OH group.
The nitrogen in the amidobenzoate resulting from the reduction with
ammonium sulphide was 4.5 p.ct.--as against 5.0 p.ct. calculated. The
moisture retained by the fibrous nitrate--nitrobenzoate--in the air-dry
state was found to be 1.97 p.ct.
The product from the structureless dibenzoate or tetrabenzoate on the
C_{12} formula, was prepared and analysed with the following results:
Calc. for
Mononitrate tetranitrobenzoate
Total Nitrogen 6.76 7.25
O.NO_{2} " 1.30 1.45
NO_{2} " (Aromatic) 5.46 5.80
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