INDUSTRIAL A-VD E-VGINEERI-VG CHE-MISTRY
August, 1926
present so much discussion. The world is now consuming about 800 tons of iodine per annum, of which more than 75 per cent comes from Chile, the remainder being extracted from seaweed in various parts of the world. The plants in Chile have a quota based on their production capacity, and the iodine is marketed through a producer’s association. The iodine section usually operates one year in each three to six, during which time enough iodine is produced to care for its quota several years in advance. One plant sometimes produces for several others if they are all owned by one company. The stored iodine is sometimes used as security for loans, so that banks as well as producers have a n interest in maintaining high prices. When the iodine section of a plant is not in operation most of the iodates go out in the tailings. This may be considered lost, for in a modern plant the tailings contain only 3 to 7 per cent nitrates, and it is unlikely that nitrate will ever sell for enough to pay the cost of reworking them. As they can contain only the iodate that was in the raw
811
material, it will always prove too costly to work them for iodine alone. Only in case of a revolution in the values of nitrates and iodine can the present tailings ever be worked again. At present not more than 2 per cent of the iodine available in the nitrate industry is being extracted. This is perhaps the most unparalleled industrial waste in the history of the world. The life of the nitrate deposits is limited, and it is doubtful if the competition from synthetic nitrates can be met for more than fifty or sixty years longer. Where will the world’s supply of iodine come from then, and what will the price be? Like every other business, the iodine industry exists to make profits. It is unreasonable to expect the producers to use their capital to store up iodine for consumption years in advance. Might not some scheme be worked out whereby governments could aid the producers and their own citizens by buying a few tons of iodine each year and storing it up for the consumption of citizens yet unborn?
A Suggested Constitutional Formula for Cellulose’~’ By Harry Le B. Gray EASTMAN RODAK Co., ROCHESTER, N. Y .
T
H E empirical formula of cellulose may be written [(COH~OO~),], where z represents the simple molecule and y the aggregate of these molecules held together by polymerization, association, or by other means unknown a t present. Herzog3 by means of X-ray analysis has shown that z must be one, two, or four. Chemical evidence as shown by viscose4 and cellulose xanthoanilide5 indicates that one hydroxyl per ‘2%is different from the other eleven hydroxyls. To bring the constitutional formula of cellulose into accord with the foregoing evidence the following is proposed : I CHzOH
1
r-CH
1
!
1
Y I H - H H 0 - C - ‘ 2 - C - C - C - C H z O H H OH OH 1 H
-
I
nL--- 7
?
I
I
- - __ __ - __ -I1
H c I
1L--c-o-c-c-c-c 1 H
H
H
H
H -C-O-LH
I
I11
It will be noted that the formuIa residues, three of which contain the the fourth the butylene. According hydroxyl of the primary alcoholic
H ~ O Ho
&,,OH
consists of four glucose amylene oxide ring and to this arrangement the group adjacent to IV
Received June 16, 1926. Communication No. 281 of the Research Laboratory of the Eastman Kodak Company. 8 Heuser, “Textbook of Cellulose Chemistry,” 1924, p. 194, translated by West and Esselen; Herzog, paper presented before the Dominion Convention of Chemists, June 2, 1926. Mitscherling, paper presented before the Division of Cellulose Chemistry, Madison, Wis., May 28, 1926; Heuser, loc cit., p . 69. 6 English Patents 231,500 to 231,811 (1924). The relationships in the xanthoanilides have been determined in the Research Laboratory of the Eastman Kodak Company, and it has been found that the ratio between C(S)SNHC,Hr and cellulose is as 1’4. 1
2
should exhibit different chemical properties from the other eleven. The preponderance of amylene oxide rings was chosen because Haworth6 has shown that the structure of normal glucose contains the amylene oxide ring. Hudson17 on the other hand, claims that the butylene oxide ring is more applicable for glucose. If this is the case the formula may be written with one amylene oxide and three butylene oxide rings. Hydrolysis a t I, 11, 111, and IV will give glucose, the butylene oxide ring probably rearranging to the amylene, thus accounting for the absence of the so-called y glucose.8 The structure is in accord with the production of 2,3,6-trimethylglucose only, as found by I r ~ i n e . Acetoly~ sis with splitting at I1 and IV mill give a theoretically quantitative yield of cellobiose octaacetate, with the necessary assumption that the butylene oxide ring shifts to the amylene. If splitting takes place a t I and 111cellobiose octaacetate and celloisobiose octaacetate or another biose octaacetate will be formed. There are four possible stereoisomers of cellobiose octaacetate, two of which are known. Ost and Knoth’3 have shown that celloisobiose octaacetat’e passes readily to cellobiose octaacetate. I n view of this celloisobiose may not be linked a t the 1,sposition but a t the 1,4 and thus be a stereoisomer of cellobiose. If this is the case the splitting a t I and I11 will give cellobiose octaacetate and another biose octaacetate. During acetolysis hydrolysis is taking place a t points I, 11, 111, and IV and simultaneously the di- and trisaccharides formed are being broken down. This probably accounts for the low yields of cellobiose octaacetate obtained. The relatively large yields of a pentaacetyl glucosell obtained from the acetolysis of cellulose appear to substantiate the above. Charlton, Haworth, and Peat, J . Chem. SOC. ( L o n d o n ) , 128, 89 (1926); Hirst, Ihid., 128, 380 (1926). 7 J . A m . Chem. Soc., 48, 1434 (1926). 8 Monier Williams, J. Chem. SOL.( L o n d o n ) , 119, SO3 (1921); Irvine and Soutar, Ibid., 117, 1489 (1920); Irvine and Hirst, Ibid., 121, 1888 (1922). 9 Irvine and Hirst, Ihid., 123, 521 (1923). 10 Cellrrlosechemie, S, 26 (1922); C. A . , 16, 2486 (1922). 11 Unpublished Research, Eastman Kodak Company, Organic Research Laboratory.
