General Carbohydrate Method

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The remaining epimer is therefore mannose. If a monosaccharide has a carbonyl function on one of the inner atoms of the carbon chain it is classified as a ketose. Dihydroxyacetone may not be a sugar, but it is included as the ketose analog of glyceraldehyde. The carbonyl group is commonly found at C-2, as illustrated by the following examples chiral centers are colored red.

As expected, the carbonyl function of a ketose may be reduced by sodium borohydride, usually to a mixture of epimeric products. D-Fructose, the sweetest of the common natural sugars, is for example reduced to a mixture of D-glucitol sorbitol and D-mannitol, named after the aldohexoses from which they may also be obtained by analogous reduction. Mannitol is itself a common natural carbohydrate. Although the ketoses are distinct isomers of the aldose monosaccharides, the chemistry of both classes is linked due to their facile interconversion in the presence of acid or base catalysts.

This interconversion, and the corresponding epimerization at sites alpha to the carbonyl functions, occurs by way of an enediol tautomeric intermediate. By clicking on the diagram , an equation illustrating these isomerizations will be displayed. Because of base-catalyzed isomerizations of this kind, the Tollens' reagent is not useful for distinguishing aldoses from ketoses or for specific oxidation of aldoses to the corresponding aldonic acids.

Oxidation by HOBr is preferred for the latter conversion. Fischer's brilliant elucidation of the configuration of glucose did not remove all uncertainty concerning its structure. Two different crystalline forms of glucose were reported in Each of these gave all the characteristic reactions of glucose, and when dissolved in water equilibrated to the same mixture. This equilibration takes place over a period of many minutes, and the change in optical activity that occurs is called mutarotation.

These facts are summarized in the diagram below. Acid-catalyzed hydrolysis of the pentamethyl ether derivatives, however, gave a tetramethyl derivative that was oxidized by Tollen's reagent and reduced by sodium borohydride, as expected for an aldehyde. These reactions will be displayed above by clicking on the diagram. The search for scientific truth often proceeds in stages, and the structural elucidation of glucose serves as a good example.

It should be clear from the new evidence presented above, that the open chain pentahydroxyhexanal structure drawn above must be modified. Somehow a new stereogenic center must be created, and the aldehyde must be deactivated in the pentamethyl derivative. A simple solution to this dilemma is achieved by converting the open aldehyde structure for glucose into a cyclic hemiacetal, called a glucopyranose , as shown in the following diagram. The linear aldehyde is tipped on its side, and rotation about the C4-C5 bond brings the C5-hydroxyl function close to the aldehyde carbon.

For ease of viewing, the six-membered hemiacetal structure is drawn as a flat hexagon, but it actually assumes a chair conformation. We can now consider how this modification of the glucose structure accounts for the puzzling facts noted above.

Qualitative Analysis of Carbohydrates - MeitY OLabs

First, we know that hemiacetals are in equilibrium with their carbonyl and alcohol components when in solution. Consequently, fresh solutions of either alpha or beta-glucose crystals in water should establish an equilibrium mixture of both anomers, plus the open chain chain form.


This will be shown above by clicking on the diagram. Note that despite the very low concentration of the open chain aldehyde in this mixture, typical chemical reactions of aldehydes take place rapidly. Second, a pentamethyl ether derivative of the pyranose structure converts the hemiacetal function to an acetal.

Acetals are stable to base , so this product should not react with Tollen's reagent or be reduced by sodium borohydride.

Carbohydrate Chemistry: Proven Synthetic Methods, Volume 2

Acid hydrolysis of acetals regenerates the carbonyl and alcohol components, and in the case of the glucose derivative this will be a tetramethyl ether of the pyranose hemiacetal. This compound will, of course, undergo typical aldehyde reactions. By clicking on the diagram a second time this relationship will be displayed above. As noted above, the preferred structural form of many monosaccharides may be that of a cyclic hemiacetal. Five and six-membered rings are favored over other ring sizes because of their low angle and eclipsing strain. Cyclic structures of this kind are termed furanose five-membered or pyranose six-membered , reflecting the ring size relationship to the common heterocyclic compounds furan and pyran shown on the right.

Ribose, an important aldopentose, commonly adopts a furanose structure, as shown in the following illustration. By convention for the D-family, the five-membered furanose ring is drawn in an edgewise projection with the ring oxygen positioned away from the viewer. The anomeric carbon atom colored red here is placed on the right.

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The upper bond to this carbon is defined as beta, the lower bond then is alpha. The cyclic pyranose forms of various monosaccharides are often drawn in a flat projection known as a Haworth formula , after the British chemist, Norman Haworth. As with the furanose ring, the anomeric carbon is placed on the right with the ring oxygen to the back of the edgewise view.

Localization of Carbohydrate-Containing Molecules

These Haworth formulas are convenient for displaying stereochemical relationships, but do not represent the true shape of the molecules. We know that these molecules are actually puckered in a fashion we call a chair conformation. Examples of four typical pyranose structures are shown below, both as Haworth projections and as the more representative chair conformers.

The anomeric carbons are colored red. Models of these glucose, galactose, mannose and allose pyranose structures may be viewed by Clicking Here. A practice page for examining the configurations of aldohexoses may be viewed by Clicking Here. The size of the cyclic hemiacetal ring adopted by a given sugar is not constant, but may vary with substituents and other structural features. Aldolhexoses usually form pyranose rings and their pentose homologs tend to prefer the furanose form, but there are many counter examples.

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  • The formation of acetal derivatives illustrates how subtle changes may alter this selectivity. By clicking on the above diagram. A pyranose structure for D-glucose is drawn in the rose-shaded box on the left.

    Carbohydrate Chemistry: Proven Synthetic Methods, Volume 2 - CRC Press Book

    Acetal derivatives have been prepared by acid-catalyzed reactions with benzaldehyde and acetone. As a rule, benzaldehyde forms six-membered cyclic acetals, whereas acetone prefers to form five-membered acetals. The top equation shows the formation and some reactions of the 4,6-O-benzylidene acetal, a commonly employed protective group.

    A methyl glycoside derivative of this compound see below leaves the C-2 and C-3 hydroxyl groups exposed to reactions such as the periodic acid cleavage, shown as the last step. The formation of an isopropylidene acetal at C-1 and C-2, center structure, leaves the C-3 hydroxyl as the only unprotected function. Selective oxidation to a ketone is then possible. Finally, direct di-O-isopropylidene derivatization of glucose by reaction with excess acetone results in a change to a furanose structure in which the C-3 hydroxyl is again unprotected. However, the same reaction with D-galactose, shown in the blue-shaded box, produces a pyranose product in which the C-6 hydroxyl is unprotected.

    Both derivatives do not react with Tollens' reagent. This difference in behavior is attributed to the cis-orientation of the C-3 and C-4 hydroxyl groups in galactose, which permits formation of a less strained five-membered cyclic acetal, compared with the trans-C-3 and C-4 hydroxyl groups in glucose.

    Derivatizations of this kind permit selective reactions to be conducted at different locations in these highly functionalized molecules. The ring size of these cyclic monosaccharides was determined by oxidation and chain cleavage of their tetra methyl ether derivatives.

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    To see how this was done for glucose Click Here. Acetal derivatives formed when a monosaccharide reacts with an alcohol in the presence of an acid catalyst are called glycosides. This reaction is illustrated for glucose and methanol in the diagram below. In naming of glycosides, the "ose" suffix of the sugar name is replaced by "oside", and the alcohol group name is placed first. As is generally true for most acetals , glycoside formation involves the loss of an equivalent of water.

    The diether product is stable to base and alkaline oxidants such as Tollen's reagent. Since acid-catalyzed aldolization is reversible, glycosides may be hydrolyzed back to their alcohol and sugar components by aqueous acid. From the structures in the previous diagram, we see that pyranose rings prefer chair conformations in which the largest number of substituents are equatorial. In the case of glucose, the substituents on the beta-anomer are all equatorial, whereas the C-1 substituent in the alpha-anomer changes to axial.

    Glycosides abound in biological systems. By attaching a sugar moiety to a lipid or benzenoid structure, the solubility and other properties of the compound may be changed substantially. Because of the important modifying influence of such derivatization, numerous enzyme systems, known as glycosidases, have evolved for the attachment and removal of sugars from alcohols, phenols and amines. Chemists refer to the sugar component of natural glycosides as the glycon and the alcohol component as the aglycon.

    Two examples of naturally occurring glycosides and one example of an amino derivative will be displayed above by clicking on the diagram. Salicin, one of the oldest herbal remedies known, was the model for the synthetic analgesic aspirin.

    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method General Carbohydrate Method
    General Carbohydrate Method

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