STRUCTURAL COMPONENTS IN METHYL VINYL SULFONE MODIFIED COTTON CELLULOSE

Methylsulfonylethyl cellulose was prepared at a low degree of substitution (0.11), which is conventional for the chemical modification of cotton, by the Michael addition of methyl vinyl sulfone to cotton fabric. The distribution of substituents in the anhydroglucose units was determined by hydrolysis of the molecular chain to glucose units, selective concentration of the substituted glucose components, gas-liquid chromatographic analyses of the methylsulfonylethylglucoses, and comparison with authentic samples of 2-O-, 3-O-, and 6-O-methylsulfonylethylglucoses in the form of trimethylsilyl ethers. The validity of each of these steps for quantitative analyses has been examined. The ratio of the 2-O-, 3-O-, and 6-O-monomethylsulfonylethylglucoses was found to be 0.20:0.03:1.0. No evidence was found for the presence of di- or tri-substituted glucoses.

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Mono-O-(methylsulfonylethy)-d-glucoses

Canadian Journal of Chemistry ◽

10.1139/v67-047 ◽

1967 ◽

Vol 45 (3) ◽

pp. 255-260 ◽

Cited By ~ 8

Author(s):

A. L. Bullock ◽

V. O. Cirino ◽

S. P. Rowland

Keyword(s):

Liquid Chromatography ◽

Acid Hydrolysis ◽

Gas Liquid Chromatography ◽

Vinyl Sulfone ◽

Methyl Vinyl ◽

Trimethylsilyl Derivatives ◽

Hydrolysis Of ◽

Methyl Vinyl Sulfone ◽

Glucose Derivatives

Mono-O-(methylsulfonylethyl)-d-glucoses needed for comparison with the cleavage products obtained by acid hydrolysis of methyl vinyl sulfone modified cotton celluloses have been prepared. Several new glucose derivatives were prepared as intermediates in the synthesis of the desired 2-O-, 3-O-, and 6-O-(methylsulfonylethyl)-d-glucoses. The reactions were monitored by gas–liquid chromatography; use was made of trimethylsilyl derivatives as necessary. The substituted glucoses were obtained as glassy solids.

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Reagent effects on distribution of methylsulfonylethyl substituents in the D-glucopyranosyl unit of cotton cellulose

Canadian Journal of Chemistry ◽

10.1139/v68-071 ◽

1968 ◽

Vol 46 (3) ◽

pp. 451-457 ◽

Cited By ~ 9

Author(s):

Stanley P. Rowland ◽

Austin L. Bullock ◽

Vidabelle O. Cirino ◽

Clinton P. Wade

Keyword(s):

Cotton Cellulose ◽

Hydroxyl Groups ◽

Vinyl Sulfone ◽

Reaction Conditions ◽

Equilibrium Conditions ◽

Methyl Vinyl ◽

Rate Controlled ◽

The Individual ◽

Methyl Vinyl Sulfone ◽

Specific Reagent

The distribution of methylsulfonylethyl substituents at the 2-O-, 3-O-, and 6-O-positions of the monosubstituted D-glucopyranosyl unit of cotton cellulose was found to be a function of the specific reagent and the reaction conditions. The distribution is dependent upon the extent to which rate or equilibrium of reaction at the individual hydroxyl groups is the controlling factor. Under conditions which approach equilibrium in the reaction of methyl vinyl sulfone with cotton cellulose, the ratio of 2-O- to 6-O-substitution is 0.14:1.0. A variety of precursors for methyl vinyl sulfone (i.e., 2-(methylsulfonyl)-ethanol, [2-(rnethylsulfonyl)ethyl]pyridinium chloride, 2-bromoethyl methyl sulfone, and to-[2-(methylsulfonyl)ethyl]ether) react with cotton cellulose under non-equilibrium conditions to generate ratios of 2-O- to 6-O-substitutions as high as 0.44:1.0. The effect of diffusion of reagents into the cotton fiber upon the distribution of substituents is clearly evident in these reactions. Specific modifications of the process of reaction of methyl vinyl sulfone or 2-(methylsulfonyl)ethanol with cotton cellulose yield ratios of substituents in the 2-O- to 6-O-positions as high as 0.8:1.0; this ratio is similar to those which characterize certain rate-controlled Williamson etherification reactions with cotton cellulose.

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