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THE RlEl'IlYLATlON OF CELLULOSE. 1735

CLXSXVI.-The Methylation of Ccllulosc.

By WILLIAM DENHAM
SMITH and HILDAWOODHOUSE
(Carnegie
Scholar).
THE correctness of the view, which has been long maintained, t h a t
the cellulose molecule is composed wholly of dextrose residues, seems
now t o have been established definitely by the work of Willstatter
and Zechmeister (Bey., 1913, 46, 2401), who, using concentrated
aqueous hydrochloric acid as the hydrolytic agent, have effected the
quantitative conversion of cellulose into dextrose. The high yields
of the acetates of dextroee and cellulose obtained by the acetolytic
method of degradation point to the same conclusion (Ost, Annaleir,
1913, 398,342). Whilst further study of the products of acetolysis
may yield an insight. into the manner of linking of the dextrose
residues in these derivatives, and therefore in the parent substance,
another method of attack on the problem of the constitution of
the polysaccharides is suggested by the results of the investigations,
still in progress, of Irvine and his collaborators on the constitution
of t h e methylated monosaccharides. If cellulose, for example, were
methylated, subsequent clcavage of the molecule should yield one
o r more of the methylated dextroses in which the niethoxyl groups
represent hydroxyl groups of the original cellulose complex, so t h a t
the nature of the linkings would be determined to an extent
dependent on the degree t o which the cellulose had been methylated
before the cleavage of the molecule.
As a first st.ep in this direction the authors attempted various
methods of rnethylating cellulose, and found t h a t the methylation
can be effected very simply by the action of methyl sulphate on the
fibrous substance after i t has been impregnated with a 15 per cent.
solution of sodium hydroxide. Under the conditions adopted, the
reaction appears t o proceed in definite stages ; thus, notwithstand-
ing the presence of sodium hydroxide in somewhat greater quantity
than that represented by the ratio C,H,,O, : 2NaOH and of excess
of methyl sulphate over t h a t required for the alkali, the composi-
tion of t h e product is t h a t of a substance of the empirical formula
C,,H,,O,=OMe. If t h e treatment with sodium hydroxide and
methyl sulphate is repeated, the new product has the compositioii
given by the formula C,HgO,*OILIe, whilst the substance produced
on a third treatment is most nearly represented by the less simple
formula C2,R3,0,5(0Me),. Similar results have been obtained in
several series of experiments. The material has not yet been
subjected to a fourth treatment. Although the products a t the
different stages can be adequately represented by such simple
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1736 DENHAM AND WOODHOUSE :

empirical formulze, and some basis for speculation regarding the

relative activity of the different hydrogen atoms in the cellulose
molecule is therefore afforded by the gradation thus indicated in the
methylation, such discussion would be premature until the homo-
geneity of the various products is more definitely established.
The methylated celluloses retain the fibrous structure of the
original material, but with increasing degree of methylation the
dried substance becomes more and more horny in appearance. The
first product, C,,H,,O,~OMe, is readily dissolved by the cuprammon-
ium solvent, the others less readily. Apparently only the first
product dissolves in a solution of zinc chloride in hydrochloric acid.
They can all be acetylated. That the methoxyl group exists in a
state of combination is shown by the high temperature (120-130O)
to which they must be heated with hydriodic acid during the
methoxyl determination by Zeisel's method before a precipitate
forms in the silver nitrate solution, and the fact is further estab-
lished by the persistence of the methoxyl group during subsequent
reactions.
The first product, C,,H,,O,*OMe, undergoes a slight change in
composition when i t is treated with a 15 per cent. solution of
sodium hydroxide alone, the recovered substance (which is less in
weight) showing a diminished percentage of carbon, hydrogen, and,
possibly, of methoxyl.
The product from the second methylation, C,H,O,*OMe, can be
converted into a xanthate by treatment with sodium hydroxide
so'lution and carbon disnlphide in it manner similar t o that in which
viscosel is prepared from ordinary cellulose. The methylated cellu-
lose regenerated from the filtered solution by warming it on the
water-bath contains slightly less methoxyl than the original
substance. The formation of this methylated viscose is of interest
in relation to the question of the relative reactivity of the hydrogen
atoms of cellulose, for, if the most reactive hydrogen atom of the
unit, C,H,,O,, is replaced in ordinary viscose from cellulose by the
-CS-SNa group, and in the methylated cellulose by the methyl
group, it is evident (i'f the compositions of the xanthates are similar)
that the xauthate from ordinary cellulose must involve in its
formation a different hydrogen atom from that which is concerned
in the formatiion of the xanthate from the methylabd cellulose.
The, inethylated celluloses, when acted on by a mixture of acetic
anhydride and acetic acid which contains a trace of sulphuric acid,
give acetyl derivatives, which are readily soluble in chloroform, and
show some resemblance to acetyl cellulose. Analyses of the products,
however, show that they contain less carbon, hydrogen, and
methoxyl t.h au would be present in complet<elyacetylated derivatives
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THE METHYLATION OF CELLULOSE. 173'7

of the methylated celluloses, but the analytical figures do not favour
the view that acetylation is incomplete. They indicate t h a t partial
elimination of the methoxyl group has occurred-accompanied
perhaps by degradation of the molecule with consequent greater
degree of acetylation than if there were no such change. Two of the
analysed samples showed signs of decomposition.

EXPERIMENTAL.
The cellulose used in the following experiments was (1) calico-a
sample of " madder " bleached calico kindly supplied by Mr. W. E.
Kay, of the Calico Printers' Association, similar t o that described
by Cross (" Researches on Cellulose," III., p. 22, No. 1) as a typical
" ncrmal " cellulose-and (2) ordinary cotton-wool. The calico was
cut up very finely and beaten under water so as to disintegrate
the fibre as far as possible, but it still contained some pieces of
fabric after this treatment.
The treatment to which the cellulose was subjected is (with minor
variations) as follows : Alkali-cellulme was prepared by leaving the
cotton for one or more days in contact with three to four times its
weight of 15-17 per cent. solution of sodium hydroxide. The
proportions of cellulose to sodium hydroxide were therefore approxi-
mately C",H,,O, : 2XaOH, but a slightly greater quantity of sodium
hydroxide was usually present. On addition of the amount of
methyl sulpiiate required to react with the sodium hydroxide,
reaction occum with evolution of heat, but when the mixture cools
i t is still alkaline, and remains so obstinately even on gentle warm-
ing, unless a considerable excess of methyl sulphate is added. The
product was washed repeatedly by decantation with distilled water,
then with very dilute alkali and acid successively, and finally with
water again. The process of washing is tedious, but was carried
out very thoroughly, especially in the portions used for analysis.
The analysed material was dried in a vacuum a t about 120° until
constant in weight. The subsequent treatments with sodium
hydroxide and methyl sulphate were carried out similarly. It was
not practicable to determine the yields when calico was used, owing
t o the pres.3nce of particles of fabric which were lem completely
inethylated than the loose fibres, but the yields of the products
from cotton-wool were determined.

First Treatment.
(A) Calico.-Fifty grams of the disintegrated material which had
been dried a t 10Go were soaked in 200 C.C. of 15 per cent. solution
of sodium hydroxide, and the mixture was allowed to' remain for
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1'738 D E N H A M A N D WOODHOUSE :

three days with frequent stirring. Fifty-two grams of methyl

sulphatel were then added instead of the 45 grams required to
react with the sodium hydroxide present. When the heat of
reaction had subsided, the mixture remained alkaline, even on
gentle warming. An additional quantity of 10 grams of methyl
sulphate was therefore added, and the mixture was shaken with
500 C.C. of benzene, b u t it was still alkaline three days later, and
when neutralised with hydrochloric acid required the equivalent
of 8 grams of sodium hydroxide f o r neutralisation. It is inadvis-
able t o use benzene as a solvent for the methyl sulphate, since a
persistent emulsion is formed ; in subsequent experiments a large
excess of methyl sulphate was used instead. The portions of the
product which still showed the structure of the fabric were separated
from the fibres.
Fnbric :
0-2975 gave 0.1043 AgI, OMe=4.63.
PiGras :
0*1212gaveOm2034 CO, and 0.0706 H,O. C=45.77; H=6*47.
0-3064 ,, 0.2350 AgI. OMe=10-14.
C1,H,,O,*OMe requires C = 46.15 ; H = 6-51; OMe = 9-29 per cent.
(B) Cottowwool.-Eighty grams of cottton-wool (dried in the
steam-oven), after remaining for three clays with 250 C.C.of 15 per
cent. solution of sodium hydroxide, were treated with 145 grams of
methyl sulphate (two and a-half times the theoretical quantity
calculated on the sodium hydroxide), when much heat was evolved.
The, yield of the washed and dried product was 90 per cent. of the
calculated amount ; t h x e was, of course, some unavoidable loss in
washing :
0.1674 gave 0.2819 CO, and 0.0964 H,O. 0,=45*93; H = 6.40.
0.2782 ,, 0.1791 AgI. OMe=8.5.
C',,H,,Q,*OMe requires C = 46.15 ; H = 6.51 ; OMe = 9.29 per cent.

Seco?Ld Treatment.
(A) Calico.-Forty-three grams of the crude product from the
first treatment were allowed t o stand for one and a-half days with
170 C.C. of 15 per cent. solution of sodium hydroxide. The,calcu-
lated guantity of methyl sulphate (reckoned on the sodium hydr-
oxide) was then added, and the mixture was thoroughly stirred.
After more than three weeks the mixture was still alkaline; it was
therefcre neutralised with hydrochloric acid, and, after washing
with water, the pieces of fabric were separated from the loose fibres.
Fabric :
0-3314 gave 0.1777 AgI. OMe=7.08.
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THE METHYLATION O F CELLULOSE. 17-33

Pi0 1"'s :
0.1338 gave 0.2330 (1.0, a i d 0.OStzC; 11,O. C = 47.49 ; 11 ==G.86.
0.3189 ,, 0.4046 AgI. OMe=16*77.
C~,I3,O,*OI1Iorequires C'-47.72 ; H = 6.82 ; OMe= 17.62 per cent,.
(B) Gotfoiz-woo/.-This preparation was carried out similarly t o
the above, except t h a t one and a-half times t h e ca.lculated quantity
of methyl sulphate was used. After remaining overnight, t h e
mixture was still alkaline, b u t was rendered acid i n reaction by t h e
addition of another equivalent of methyl sulphate. The yield was
80 per cent. of the calculated amount:
0.1640 gave 0.2895 CO, and 0*1015 H,O. C=48.14; H=6.88.
0.3466 ,, 0.5176 Agl. OMe=19.72.
C,1I,O4*OMe requires C =47*72; H = 6.82; OMe= 17.62 per cent.

Third Treatment .
(A) Calico.-The Ioose fibres only were treated further. These
wheii dry formed a horny mass, which was penetrated by the sodium
hydroxide solutioii with difficulty. Two distinct preparations
were carried out, the quantities used being i n (1) 12 grams of t h e
twice methylated substance, 33 C.C. of 17 per cent. solution of
sodium hydroxide and 30 grams of methyl sulphate, and in
(2) 2 grams of the twice methylated substance, 8 C.C. of 15 per
cent. solution of sodium hydroxide arid 12 grams of methyl
sulphate :
(I) 0.1810 gave 0.3122 GO, and 0*1100 H,O. C=47*04; H = 6.75.
0.1600 ,, 0.2782 CO, ,, 0.0979 H20. C=47*42; H=6*80.
0.2645 ,, 0.4310 AgI. OMe=21-53.
(2) 0.1359 ,, 0.2409 CO, and 0.0845 H20. C=48*34; H = 6 * 9 1 .
0.3056 ,, 0.5114 -4gI. OMe=22*11.
C24H,,0,5(0Me), requires C'=48*47;H = 6.96 ;OMe = 21.59 per cent.
(B) Cotton-wool.-Twenty grams of t h e twice methylated sub-
stance, after remaining for two days i n contact with 54 C.C. of
17 per cent. solution of sodium hydroxide, were treated with
11 grams of methyl sulphat4e. The yield was 73 per cent. of t h e
calculated amount :
0.1892 gave 0-3355 CO, and 0-1223 H,O. C=45*36; H=7.18.
0.2799 ,, 0.5760 AgI. ORle=23'3.
C,,H3,0,,(0Me), requires C = 48.47 ;H = 6.96 ;OMe = 21 -59 per cent.

Action of Sodium Egdroxide o n t h e Prodztct f r o m the First

Methylation of Cot ton-wool.
Two grams of the methylated product, dried a t looo, were allowed
t o remain for four days iii contact with 8 C.C.of 15 per cent. solution
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1740 DENHAM AND WOODHOUSE :

of sodium hydroxide. After washing with water and drying, the

substance weighed 1-68 grams :
0.1430 gave 0.2382 CO, and 0'1430 H,O. C = 45-43; H = 6.29.
0.1680 ,, 0.2780 CO, ,, 0.1017 H,O. C'=45.13; H=6.01.
0-1715 ,, 0-1013 AgI. OMe=7-8.
The composition before treatment wsts : C'=45*83; H = 6-44 ;
OMe= 8.5. The washings after concentration on the water-bath
were found to reduce Fehling's solution.

Conversion of the Twice Methylated Product f r o m Cotton-wool i ~ z t o

a Xanthate.-Regeneration of the Methyluted Cellulose.
Eight grams of carbon disulphide were added to a mixture of
10 grams of the methylated cellulose and 30 grams of an 18 per
cent. solution of sodium hydroxide which had been in contact with
each other for twenty-four hours, and the whole was allowed t o
remain for six hours in a stoppered bottle with frequent stirring.
After exposure to the air f o r a few minutes t o remove any excem
of carbon disulphide, the mass was brought into solution by
prolonged stirring with 30 C.C. of an 18 per cent. solution of sodium
hydroxide. The solution after dilution with about 2 litres of water
was filtered through nickel gauze, and finally through filter paper-
a slow process owing to the presence of undissolved gelatinous
matter. The methyl cellulose regenerated by heating the solution
on the water-bath ww washed by decantation with large quantities
of water. In a second experiment the procedure was similar,
except that 90 C.C. of the sodium hydroxide solution were used to
dissolve the reaction product :
I. 0.2659 gave 0'2834 AgI. OMe = 14.08.
11. 0-2046 ,, 0-2423 AgI. OMe=15*64.
The methylated cellulose used contained OMe= 19.72 per cent.

Acetylataon of the Methyluted Celluloses derived from

Cotton-wool.
The procedure was similar in each case; 2 grams of the methylated
cellulolse were treatsd with a mixture of 8 grams of acetic anhydride,
8 grams of acetic acid, and a trace of sulphuric acid. The mass
was stirred continuously for an hour, the temperature being kept
below 30°. After the mixture had remained for about twelve hours
a t the ordinary temperature, with occasional stirring, it was warmed
to 35O for a few m i n u k , then diluted with acetic acid, and filtered
through a perforated plate to remove the small quantity of undis-
solved matter. The acetyl compound was precipitated by pouring
the solution into water, and was washed with water until the
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THE METEYLATION OF CELLULOSE. 1741

particles had no longer an acid reaction. The film deposited on the

evaporation of a chloroform solution was analysed after i t had
been dried in a vacuum at about 90° until the weight was constant.
The films of the substances nbmbered I and I1 below were coloured,
evidently owing to slight decomposition ; t h a t from substance I1 I
was colourless. The acetic acid was determined by dissolving the
acetyl compound in a mixture of equal volumes of sulphuric acid
and water and subsequent distillation with steam. From the alkali
required for the distillate during the first four hours was deducted
that required for the second four hours' distillate, which was taken
to represent the amount required to neutralise the volatile acid
derived from the decomposition of the molecule assumed constant
throughout (Schliemann, Annalen, 1911, 378, 368). Substance I
required 14-66 C.C. NIZ-NaOH for the first period and 3.52 C.C.
NIZ-NaOH for the second period; for substance I1 the quantities
of N/Z-NaOH required were 12.30 C.C. and 3.36 C.C. With sub-
stance I11 the method failed as the amount of alkali required was
the same f o r each period. The results for substances I and I1 may
therefore be untrust'worthy.

I . Acetyl Derivative fronz the First Methylation Product.

0.1802 gave 0.3026 CO, and 0.0869 H,O. C = 45.79 ; H = 5.36.
0.3560 ,, 0.1070 AgI. OMe=3'97.
0.6066 ,, 0.3342 C,H,O,. C2H,0,=55*09.
C,,H,,(CH,.C'O),O,.Ohle requires C= 50.36 ; H = 5-84; OMe =5-66;
C2H40,= 54.74 per cent.

11. Acetyl Derivative from, the Second Methylation Product.

0.1461 gave 0.2467 CO, and 0'0712 H,O. C=46*05; H =5.38.
0.3202 ,, 0.1469 AgI. OMe=6.06.
0-5025 ,, 0.2682 C2H,0,. C?,H,O, = 53.43.
C,H7(CH3*CO),04*OMerequires C = 50.97 ; H = 6.02 ; OMe = 11.29 ;
(.&H40,=46'15 per cent.

111. Acetyl Derivative from the Third Methylation Product.

0.1954 gave 0.3460 CO, and 0*1024 H20. C'= 48.29 ; C = 5.83.
0.2954 ,, 0-2800 AgI. OMe=12*7.
C~4H28(CH3-C0)70,5(OMe)5 requires C = 50.99 ; H = 6-31;
OMe= 15-32 per cent.*
* During the progress of this work, and after most of the results just
recapitulated had been reported to the Carnegie Trust, an abstract of a patent
dealing with similar problem was published (J. SOC.Chenz. hd.,1913, 38, 420). In
the fnll specification (French Patent 447,974, published 20th January, 1913)
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1742 ANNUAL REPORT OF THE 1NTERNATlONAL

Tile autliors desire t o express their tliariks t o Professor Irvine for

tlie helpful iriterest he lias taken in this work, arid to’ the Carnegie
Trust for its contribution to the cost,
RESEARCHLABORATORY,
CHEMICAL,
UNTTEI)
COLLEGE AND Sr. LEoxnieri,
OF S,r. SALVATOR
UNIVEI’.M~TY
OF ST. ANDREWS.