Mono-<i>O</i>-(methylsulfonylethy)-<scp>d</scp>-glucoses

Bullock, Austin L.; Cirino, Vidabelle O.; Rowland, Stanley P.

doi:10.1139/v67-047

Cited by 9 publications

(3 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Four liquid phases have proven most useful for the columns in our studies: these are SE-52, XE-60, QF-1, and Apiezon M. Each chemical modification of glucose generated specific requirements for columns and other techniques as indicated in the following sections. Methylsulfonylethyl Cotton [3,14] The base-catalyzed reaction of cotton fabric with methyl vinyl sulfone is a reversible nucleophilic attack of the alkoxide ions of the cellulose on the vinyl group (Fig. 2).…”

Section: Utilization Of Model Compoundsmentioning

confidence: 99%

See 1 more Smart Citation

The Relative Reactivities of the Hydroxyl Groups of Cotton Cellulose—A Progress Report1

Rowland

Bullock

Cirino

et al. 1967

Textile Research Journal

View full text Add to dashboard Cite

Major preceding studies of the distribution of substituents in cellulose have been reviewed. Over-all results indicate that the highest degree of reaction occurs at the hydroxyl group on C-2 in the case of the irreversible Williamson syntheses involving reagents of small molecular size. Pronounced preferential reaction occurs at the hydroxyl group on C-6 in the case of reversible reactions and with increasing molecular size of reagent.The relative reactivities of the hydroxyl groups on C-2, C-3, and C-6 of the D (1→4)-β-glucopyranosyl unit of cotton cellulose have been explored with three chemical agents.Predominant reaction of cotton cellulose occurs at the primary hydroxyl group on C-6 in the case of the reversible Michael addition of methyl vinyl sulfone (i.e., 2-0-: 3-0-: 6-0-= 0.20: 0.03: 1.00), at the hydroxyl groups on C-2 and C-6 in the case of the irreversible reaction with diethylaminoethyl chloride (1.27 : 0.35 : 1.00), and at the hydroxyl groups on C-6 and C-2 in the case of the irreversible Williamson synthesis with sodium allyl sulfate (0.7:0.2:1.0). The D -(1→4)-α-glucopyranosyl unit of dextrin (employed as a soluble model compound for cellulose) undergoes reversible esterification with formic acid most rapidly and to the highest equilibrium level at the primary hydroxyl group on C-6.-

show abstract

Section: Utilization Of Model Compoundsmentioning

confidence: 99%

“…Several studies reported here have relied heavily on these techniques. , This report summarizes a series of recent explorations in measurements of the relative distributions of substituent groups on the 2-0-, 3-0-, and 6-0-positions of the D-glucohyranosyl unit [3,7,12,13,14]. To put this work in proper perspective, major .…”

Section: Introductionmentioning

confidence: 99%

The Relative Reactivities of the Hydroxyl Groups of Cotton Cellulose—A Progress Report1

Rowland

Bullock

Cirino

et al. 1967

Textile Research Journal

View full text Add to dashboard Cite

show abstract

“…Gigg and Cunningham (2,3) and Montgomery and Thomas (4) discussed the removal of this group. Bullock and co-workers (1) indicated that this group was more satisfactory than the benzyl group, since it was more readily removed after the condensation reaction was complete. Experimental…”

Section: Introductionmentioning

confidence: 99%

The synthesis and identification of allyl ethers of glucose and cellulose

Hoiness¹,

Wade²,

Rowland³

1968

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Substituent group distribution in ally1 cellulose, resulting from the base-catalyzed condensation of sodium allyl sulfate with cotton cellulose and having a degree of substitution of 0.07, was found to be 0.7: 0.2:l.O in the 2-0-, 3-0-, and 6-0-positions of the anhydroglucose units. Several new glucose derivatives were prepared in the syntheses of the 2-0-, 3-0-, and 6-0-allyl-D-glucoses.Canadian Journal of Chemistry, 46, 667 (1968) Introduction As a part of a program to characterize the reactivities of the hydroxyl groups of the Dglucopyranosyl units of cotton cellulose toward mono-and polyfunctional reagents, we have studied the substituent group distribution resulting from the base-catalyzed condensation of sodium allyl sulfate with cotton cellulose. In order to identify the 2-0-, 3-0-, and 6-0-allyl-Dglucoses obtained from the hydrolytic cleavage of the molecular chain of the modified cotton cellulose, it has been necessary to synthesize and characterize several new derivatives of glucose. These were prepared by the nucleophilic substitution reaction on allyl bromide with the alkoxide group of a selected glucose derivative. Substituent groups on glucose hydroxyls which were stable to the conditions of the reactions, yet easily removed by acid hydrolysis after introduction of the allyl group, were employed to block all the hydroxyl groups which were to be free in the final product. The requirement of stable blocking groups in basic reaction media for the preparation of 2-0-, 3-0-, and 6-0-substituted

show abstract