Synthesis of Chlorodeoxycellulose and its Conversion to 5,6-Cefluloseen

Abstract

Reaction of cellulose acetate with methylsulfonyl chloride in N,N-dimethylformamide has been studied under different conditions of time, temperature and concentration of the reagent. Using this method, chlorodeoxycellulose of a D.S. as high as 0.58 has been prepared. The reaction has also been applied to purified cotton linters to yield chlorodeoxycellulose. Attempts to prepare this cellulose derivative by reaction of cellulose acetate with acetyl chloride, anhydrous aluminum chloride and magnesium chloride in N,N-dimethylformamide were unsuccessful.

5, 6-celluloseen is obtained by dehydrohalogenation of the chlorodeoxycelluloses either with dry methanolic potassium hydroxide or with potassium tert. butoxide in dimethyl sulfoxide. With the latter reagent the conversion of chloro deoxycellulose to celluloseen is almost quantitative.

Keywords

Chlorination dehydrohalogenation unsaturation. Cellulose acetate purified cotton linters purified activated cotton linters. Chlorodeoxycellulose chlorodeoxycellulose acetate 5,6-celluloseen. Methylsulfonyl chloride acetyl chloride anhydrous aluminum chloride magnesium chloride dimethylformamide dimethylsulfoxide methanolic potassium hydroxide potassium tert. butoxide. Degree of substitution chlorine acetyl value intrinsic viscosity bromine numher double honds mechanism-iminium salt.

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References

Albright, J.D. , Benz, E. , Lanzilotti, A.E. , and Goldman, L. , Reactions of Sulfonyl Chloride N,N-Dimethylformamide Complexes, Chem. Comm. 413-415 (1965).

Boehm, R.L. , Chlorination of Cellulose with Thionyl Chloride in a Pvridine Medium. J. Org. Chem. 23, 1716-1720 (1958).

Carré, P. and Mauclère, P. , The Transformation of Complex Alcohols into the Corresponding Mono- and Poly-Chlorohvdrins by Means of Thionyl Chloride, Comple. rend. 192, 1567-1569 (1931).

Dauben, W.G. , in "Organic Synthesis," Vol. 45, New York, John Wiley and Sons, Inc., 1965, p. 33.

Dimitrov. D.G. , Galbraikh, L.S. , and Rogovin, Z.A. , A Synthesis of New Industrial Cellulose Performed by Introducing Double Link in the 5,6-Cellulosc Molecule Cellulose Chem. Technol. 2, 375 389 (1968).

Evans, M. , Long, L. , Jr., and Parrish, F.W. , Reaction of Carbohydrates with Methylsulfonyl Chloride in N,N-Dimethylformamide. Preparation of some Methyl 6-Chloro-6-deoxyglycosides , J. Org. Chem. 33, 1074-1076 (1968 ).

Fumasoni, S. and Schippa. G. , Chlorination of Cellulose with Thionyl Chloride , Ann. Chim. (Rome) 55, 894-900 (1963).

Hall H.K. , Jr., Kinetics of Reactions of Acyl Chlorides. Solvolysis of Acyl Halides in Dimethylformamide, J. Amer. Chem. Soc. 78, 2717-2719 (1956).

Hess, K. and Ljubitsch, N. , Cellulose. (LI)-Esterification of Cellulose with Tosyl Chloride in the Presence of Pyridine, Ann. 507, 62-69 (1933).

10.

Polyakov, A.I. and Rogovin, Z.A. , Synthesis of New Cellulose Derivatives . XXIII: Synthesis of Chlorocellulose and its Conversion of Amino- and Nitrilo-Cellulose, Vysokomol. Soedin. 5, 11-17 (1963) and PolymerSci., USSR 4, 610-618 (1963).

11.

Roberts R., The Esterification of Cellulose with Methylsulfonyl (Mesyl) Chloride, J. Amer. Chem. Soc. 79, 1175-1182 (1957).

12.

Schwenker, R.F. , Jr., and Pacsu , E. , Chemically Modifying Cellulose for Flame Resistance, Ind. Eng. Chem. 50, 91-96 (1958).

13.

Siggia, S. , in "Quantitative Organic Analysis Via. Functional Groups," New York, John Wiley and Sons, Inc., 1949, p. 11.

14.

Sletkina, L.S. and Rogovin, Z.A. , Structure and Properties of Cellulose and its Derivatives. Possibility of Preparation of Fluorodeoxycellulose, Vysokomol. Soedin., Ser. B. 9(1), 37-39 (1967); C.A. 66, 7254 (1967).

15.

Srivastava, H. C., Harshe, S. N., and Srivastava, V. K., unpublished data.

16.

Steyermark, A. , in "Quantitative Microanalysis," New York, Academic Press, 2d ed., 1961, pp. 287, 316, 444.

17.

Tipson, R.S. , "Infrared Spectroscopy of Carbohydrates," National Bureau of Standards Monograph 110, 7 (1968).

18.

Vigo, T.L. and Welch, C.M. , Fibrous Chlorodeoxycellulose Yarn. Its Preparation, Properties, and Reaction with Nucleophilic Sulfur and Nitrogen Compounds, Textile Res. J. 40, 109-115 (1970).

19.

Wolfrom, M.L. , Sowden, J.C. , and Metcalf, E.A. , Mesylatecl Cellulose Derivatives, J. Amer. Chem. Soc. 63, 1688-1697 (1941 ).