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The mechanism of oxidation of cellulose by atmospheric oxygen in an alkaline medium. A study of the chemical composition of the oxidation products
1592
~ . S. MAY-ATet al.
(3) Fission of a salt of 7-vinylpyridine by an amine has yielded a compound that has not been reported previously--the dianil of 7-vinylglutaconic dialdehyde. (4) The dianil of 7-vinylglutaconic dialdehyde does not polymerize by the action of BF 3 or under irradiation. Translated by E. O. P]tILLIPS
REFERENCES 1. 2. 3. 4. 5.
F. ZINCKE, Liebigs. Ann. 330: 361, 1904; 338: 107, 1905 W. K(~NIG, Prakt. Chem. 69; [2], 105, 1904; 70: [2], 19, 1904 A. F. VOMPE, Dissertation, 1951 F. M. HAMER and R. J. RATHBONE, J. Chem. Soc. 960, 1947 N. E. GRIGOR'EVA and V. I. KOVALENKO, Ueh. zap. Khar'kovskogo gos, u n - t a 3: 87, 1950 6. O. BAUMGARTEN, Ber. 59: 1168, 1926 7. O. BAUMGARTEN, Ber. 64: 1045, 1931 8. N. E. GRIGOR'EVA, Tr. khim. fak-ta i nauehno-issled, in-ta khimii K h G U 18: 209, 207
THE MECHANISM OF OXIDATION OF CELLULOSE BY ATMOSPHERIC OXYGEN IN AN ALKALINE MEDIUM. A STUDY OF THE CHEMICAL COMPOSITION OF THE OXIDATION PRODUCTS * N . S. MAYAT, O. P . GOLOVA a n d I . I . N I K O L A Y E V A I n s t i t u t e of Macromolecular Compounds, U.S.S.R. Academy of Sciences (Received 6 December 1961)
IN A study of the mechanism of decomposition of cellulose, and of models of closely similar structure by the action of atmospheric oxygen in an alkaline medium we have shown, in collaboration with other authors, that the cellulose passes into solution and the quantity of dissolved cellulose depends not only on the conditions of oxidation but also mainly on its physical structure. For cellulose hydrate this quantity is 20 %, but for cotton cellulose it is 2-3 % of the weight of the dry material (after oxidation for 5 hours at 100° in 1 ~/o NaOH solution). The problem of by what processes and in the form of what alkaline-oxidation decomposition products one form or another of cellulose passes into solution as yet remains unsolved. * Vysokomol. soyed. 5: No. 6, 873-874, 1963.
Oxidation of cellulose
1593
With the object of examining this problem, in the present work we have studied the composition of the soluble products of the alkaline-oxidative degradation of cellulose hydrate. This investigation was based mainly on paper chromatography. Soluble decomposition products were isolated from the continuous oxidation of cellulose hydrate by atmospheric oxygen under the above conditions. After treatment of the alkaline solution with a cation exchange resin, removal of volatile products by distillation and evaporation to dryness, the dry residue constituted 20% of the weight of the original cellulose hydrate. On treatment of the residue with water 16.4% went into solution and 3.6% was soluble only in dilute alkalis. Titration of the aqueous solution of decomposition products showed the presence of 18.9 rag-equiv, of acids (including lactones), corresponding to 1.89 mg-equiv, of acids per gramme of oxidized cellulose hydrate. Chromatographic analysis of the soluble decomposition products (shown with a mixture of butanol, pyridine and water, 4 0 : 3 8 : 2 2 , development with silver nitrate and universal indicator) showed that they contain high-molecular substances (R/=0.25)--mainly triose, tetrose and p e n t o s e - - a n d low-molecular neutral (Rf=0.86) and acidic (/?:-----0.94 and R:=0.50--1ong strip) compounds. Chromatographic separation of the decomposition products with a mixture of ethyl acetate, acetic acid and water, 10 : 1-3 : 1 (development with universal indicator and hydroxylamine containing ferric chloride) and comparison with published R L figures, showed the presence of the following acids: lactic (RL=I), glycollic (R~=0.73), dihydroxybutyric (RL=0.58), the laetone of dihydroxybutyric (R~=l.04) and D-glucosaccharinic (R~=0.56). These acids and lactones have been identified previously among the products of decomposition of cellulose with a reduced end group, in an alkaline medium [1]. CONCLUSIONS
(1) Oxidation of cellulose hydrate by atmospheric oxygen in an alkaline medium yields soluble degradation products in the quantity of 20 % of the original material. (2) The degradation products consist of both water-soluble oligosaccharidcs (mainly cellotriose, cellotetrose and cellopentose) and low-molecular, acidic and neutral degradation products (mainly saccharinie acids and their lactones). Translated by E. O. PHILLIPS
REFERENCE 1. C. MACHELLand G. N. RICHARD, J. Chem. Soc. 1924, 1960
~ . S. MAY-ATet al.
(3) Fission of a salt of 7-vinylpyridine by an amine has yielded a compound that has not been reported previously--the dianil of 7-vinylglutaconic dialdehyde. (4) The dianil of 7-vinylglutaconic dialdehyde does not polymerize by the action of BF 3 or under irradiation. Translated by E. O. P]tILLIPS
REFERENCES 1. 2. 3. 4. 5.
F. ZINCKE, Liebigs. Ann. 330: 361, 1904; 338: 107, 1905 W. K(~NIG, Prakt. Chem. 69; [2], 105, 1904; 70: [2], 19, 1904 A. F. VOMPE, Dissertation, 1951 F. M. HAMER and R. J. RATHBONE, J. Chem. Soc. 960, 1947 N. E. GRIGOR'EVA and V. I. KOVALENKO, Ueh. zap. Khar'kovskogo gos, u n - t a 3: 87, 1950 6. O. BAUMGARTEN, Ber. 59: 1168, 1926 7. O. BAUMGARTEN, Ber. 64: 1045, 1931 8. N. E. GRIGOR'EVA, Tr. khim. fak-ta i nauehno-issled, in-ta khimii K h G U 18: 209, 207
THE MECHANISM OF OXIDATION OF CELLULOSE BY ATMOSPHERIC OXYGEN IN AN ALKALINE MEDIUM. A STUDY OF THE CHEMICAL COMPOSITION OF THE OXIDATION PRODUCTS * N . S. MAYAT, O. P . GOLOVA a n d I . I . N I K O L A Y E V A I n s t i t u t e of Macromolecular Compounds, U.S.S.R. Academy of Sciences (Received 6 December 1961)
IN A study of the mechanism of decomposition of cellulose, and of models of closely similar structure by the action of atmospheric oxygen in an alkaline medium we have shown, in collaboration with other authors, that the cellulose passes into solution and the quantity of dissolved cellulose depends not only on the conditions of oxidation but also mainly on its physical structure. For cellulose hydrate this quantity is 20 %, but for cotton cellulose it is 2-3 % of the weight of the dry material (after oxidation for 5 hours at 100° in 1 ~/o NaOH solution). The problem of by what processes and in the form of what alkaline-oxidation decomposition products one form or another of cellulose passes into solution as yet remains unsolved. * Vysokomol. soyed. 5: No. 6, 873-874, 1963.
Oxidation of cellulose
1593
With the object of examining this problem, in the present work we have studied the composition of the soluble products of the alkaline-oxidative degradation of cellulose hydrate. This investigation was based mainly on paper chromatography. Soluble decomposition products were isolated from the continuous oxidation of cellulose hydrate by atmospheric oxygen under the above conditions. After treatment of the alkaline solution with a cation exchange resin, removal of volatile products by distillation and evaporation to dryness, the dry residue constituted 20% of the weight of the original cellulose hydrate. On treatment of the residue with water 16.4% went into solution and 3.6% was soluble only in dilute alkalis. Titration of the aqueous solution of decomposition products showed the presence of 18.9 rag-equiv, of acids (including lactones), corresponding to 1.89 mg-equiv, of acids per gramme of oxidized cellulose hydrate. Chromatographic analysis of the soluble decomposition products (shown with a mixture of butanol, pyridine and water, 4 0 : 3 8 : 2 2 , development with silver nitrate and universal indicator) showed that they contain high-molecular substances (R/=0.25)--mainly triose, tetrose and p e n t o s e - - a n d low-molecular neutral (Rf=0.86) and acidic (/?:-----0.94 and R:=0.50--1ong strip) compounds. Chromatographic separation of the decomposition products with a mixture of ethyl acetate, acetic acid and water, 10 : 1-3 : 1 (development with universal indicator and hydroxylamine containing ferric chloride) and comparison with published R L figures, showed the presence of the following acids: lactic (RL=I), glycollic (R~=0.73), dihydroxybutyric (RL=0.58), the laetone of dihydroxybutyric (R~=l.04) and D-glucosaccharinic (R~=0.56). These acids and lactones have been identified previously among the products of decomposition of cellulose with a reduced end group, in an alkaline medium [1]. CONCLUSIONS
(1) Oxidation of cellulose hydrate by atmospheric oxygen in an alkaline medium yields soluble degradation products in the quantity of 20 % of the original material. (2) The degradation products consist of both water-soluble oligosaccharidcs (mainly cellotriose, cellotetrose and cellopentose) and low-molecular, acidic and neutral degradation products (mainly saccharinie acids and their lactones). Translated by E. O. PHILLIPS
REFERENCE 1. C. MACHELLand G. N. RICHARD, J. Chem. Soc. 1924, 1960