Die Konstitution der Dimethylen‐glucose Lobry de Bruyns und der Monomethylen‐glucose von Tollens

Schmidt, Otto; Distelmaier, Alfred; Reinhard, Hans

doi:10.1002/cber.19530860617

Cited by 23 publications

(2 citation statements)

References 11 publications

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“…Dimethylene glucose, the structure of which has recently bee11 show11 to be 1,2;3,5-di-0-methylene-~-glucofura110se (13,14), has been used for the introduction of substituents in the 6-position of glucose (3,9). Treatment of this derivative with dispersed sodium in dioxane gave the corresponding sodio derivative which, upon reaction with methyl bromoacetate, yielded 6-0-carboxymethyl-1,2;3,5-di-0-methylei~e-~-glucofurai~ose methyl ester in the crystalline form.…”

Section: And Discussionmentioning

confidence: 99%

Synthesis of Four Carboxymethyl Ethers of Glucose

Shyluk¹,

Timell²

1956

Can. J. Chem.

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The 2-, 3-, and 6-0-carbosymethyl-D-glucoses and the 2,3-di-0-carboxymethyl-D-glucose have been synthesized. A solvent system was found which gave complete paper chromatographic separation of these derivatives as well as of those obtained upon hydrolysis of a carboxymethylcellulose.The physical and chemical properties of partially substituted cellulose derivatives cannot be explained only in terms of molecular weight, polymolecularity, and degree of substitution, the distribution of the substituents along the chain molecules of cellulose also having to be considered. Various approaches in such distribution studies have been used, the most direct of which involves quantitative paper chromatography. Brownell (3) appears to have come the closest t o a successful application of such a method in his work on hydroxyethylcellulose. However, in this study, as well as in similar work on methylcellulose (1, 8, l l ) , most of the isomeric mono-and di-substituted derivatives of glucose could not be separated.Previous investigations on carboxymethylcellulose (6, 12, 15, 16) have indicated the desirability of a more direct approach and this study was undertaken to develop the quantitative paper chromatographic technique for this purpose. Three stages had to be considered in this connection, namely hydrolysis of the carboxyrnethylcellulose, separation and identification of the various carboxymethylated glucoses in the hydrolyzate, and the quantitative determination of these glucose derivatives.The hydrolysis of carboxymethylcellulose and the stability of the carboxymethyl group to the coilditions of acid hydrolysis have been previously investigated (15). For separation and identification of the seven possible carboxymethyl derivatives of glucose which conceivably could be formed by hydrolysis of a partially substituted carboxymethylcellulose, it was necessary to have these seven compounds available. The present study deals with the synthesis and separation of the 2-, 3-, and 6-0-carboxymethyl-D-glucoses and the 2,3-di-0-carboxymethyl-D-glucose. RESULTS AND DISCUSSIONThe general procedure used for introducing the carboxymethyl groups in the desired positions was t o allow methyl bromoacetate t o react with the sodio compound, prepared by the reaction of metallic sodium with a glucose derivative having the appropriate hydroxyl groups unsubstituted. For the preparation of the sodio derivative, advantage was taken of the greater chemical reactivity of sodium dispersions (2). Such dispersions consist of a stable sus-'Manz~script

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Section: And Discussionmentioning

confidence: 99%

Synthesis of Four Carboxymethyl Ethers of Glucose

Shyluk¹,

Timell²

1956

Can. J. Chem.

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“…T h e most suitable compound from which t o attempt a synthesis of glucose-6-S-methyl xanthate appeared t o be the di-0-methylene glucose-6-acetate synthesized by Hough, Jones, and Magson (7), which was characterized as the 1,2;3,5-di-0-acetal by Schmidt, Distelmaier, and Reinhard (17) and later by Shyluk, Honeyman, and Timell (18). T h e replacement of the 0-acetyl group by a sodium atom proceeded smoothly in alcoholic sodium hydroxide, and subsequent treatments with carbon disulphide and with methyl iodide produced the new, crystalline 1,2;3,5-di-0-methylene glucofuranose-6-Smethyl xanthate (111) in 84% yield.…”

Section: Introductionmentioning

confidence: 99%

Some Xanthate Methyl Esters of Glucose

Sanyal¹,

Purves²

1956

Can. J. Chem.

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Intramolekulare Wasserstoffbrücken in substituierten Gluco‐ bzw. Fructopyranosen und ‐furanosen

Bartsch¹,

Prey²

1968

Justus Liebigs Ann. Chem.

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Verschiedene Acetale von Gluco-bzw. Fructopyranosen und -furanosen sowie Hydroxytetrahydrofuran-bzw. Hydroxytetrahydropyran-Derivate (Tab. 1 ) werden mit Hilfe von 1Rspektren auf das Vorhandensein und die Lage von intramolekularen Wasserstoffbrucken untersucht (vgl. Aufstellung S. 203). Bei unseren Untersuchungen uber die Konfiguration von Zuckern und Zucker-Derivaten interessierte uns auch die Moglichkeit der Ausbildung von intramolekularen Wasserstoff-Brucken und ihre Lage im Zucker-Molekul. Schon 1957 beschrieb Konkin 1) die verschiedenen Moglichkeiten von Wasserstoffbriicken in Zuckern, und 1959 wurden die ersten Infrarot-Untersuchungen uber Wasserstoffbriicken an Zucker-Modellsubstanzen ausgefuhrt 2). ~ Im Infrarotspektrum wird, da beim Vorhandensein von Wasserstoffbriicken die OH-Bindungslange zunimmt, die Absorptionsbande der OH-Valenzschwingung nach niedrigeren Frequenzen verschoben. Aus der GroRe dieser Verschiebung kann auf die Starke der Wasserstoff brucke geschlossen werden.Den 0 -H . . . 0-Abstand (L) einer intramolekularen Wasserstoffbriicke in Abhangigkeit von der Wellenzahlverschiebung Av berechnet Kuhn 3) nach der empirischen Beziehung (I), die jedoch nur fur intramolekulare Wasserstoff briicken zwischen zwei Hydroxyl-Gruppen in Tetrachlorkohlenstofflosung gilt. Eine Wasserstoffbrucke liegt nur d a m vor, wenn der Abstand L t3.3 A ist. Methodik Die Spektren wurden in einer Kiivette mit variabler Schichtdicke mit dem Infrarot-Gitter-Spektrophotometer 125 (Fa. Perkin-Elmer, Uberlingen) in CC14 (Uvasol, Fa. E. Merck, Darmstadt) in 0.5-0.001 m Losungen bei Schichtdicken von 0.5 -3.0 mm gemessen.

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Die Konstitution der Dimethylen‐glucose Lobry de Bruyns und der Monomethylen‐glucose von Tollens

Cited by 23 publications

References 11 publications

Synthesis of Four Carboxymethyl Ethers of Glucose

Synthesis of Four Carboxymethyl Ethers of Glucose

Some Xanthate Methyl Esters of Glucose

Intramolekulare Wasserstoffbrücken in substituierten Gluco‐ bzw. Fructopyranosen und ‐furanosen

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