Aldose aldehydes

Just as the Kiliani-Fischer synthesis lengthens an aldose chain by one carbon, the Wohl degradation shortens an aldose chain by one carbon. The Wohl degradation is almost the exact opposite of the Kiliani-Fischer sequence. That is, the aldose aldehyde carbonyl group is first converted into a nitrile, and the resulting cyanohydrin loses HCN under basic conditions—the reverse of a nucleophilic addition reaction. 

Aldehydes - Compounds RC(=0)H, in which a carbonyl group is bonded to one hydrogen atom and to one R group. [5] Aldoses - Aldehydic parent sugars (polyhydroxyaldehydes H[CH(0H)] C(=0)H, >1) and their intramolecular hemiac-etals. [5]... 

SchifT s reagent A solution of rosaniline in water decolorized with sulphurous acid. Aliphatic aldehydes and aldose sugars give a magenta colour with this reagent with aromatic aldehydes and aliphatic ketones the colour develops more slowly aromatic ketones do not react. 

Carbohydrates may be divided into monosaccharides, disaccharides and polysaccharides. The monosaccharides under certain conditions react as polyhydroxy-aldehydes or polyhydroxy-ketones two important representatives are glucose CjHjjO (an aldose) and fructose (laevulose) CgHuO, (a ketose). Upon hydrolysis di- and polysaccharides 3deld ultimately monosaccharides. Common disaccharides are sucrose, lactose and maltose (all of molecular formula C,2H2. 0,), whilst starch, dextrin and cellulose, (CjHjoOj), in which n > 4, are typical polysaccharides. 

The simple sugars or monosaccharides are polyhydroxy aldehydes or ketones, and belong to Solubility Group II. They are termed tetroses, pentoses, hexoses. etc. according to the number of carbon atoms in the long chain constituting the molecule, and aldoses or ketoses if they are aldehydes or ketones. Most of the monosaccharides that occur in nature are pentoses and hexoses. 

Both aldoses and ketoses reduce Fehling s solution (for details, see under 4). This fact may appear surprising when it is remembered that Fehling s solution is one of the reagents for distinguishing between aldehydes and ketones (see 4). The explanation lies in the fact that a-hydroxyketones are much more readily oxidised than simple ketones, perhaps because the hydroxy ketone allows its isomerisation, in the presence of alkali, into an aldehyde. For example, fructose, a keto-hexose, might Isomerlse thus ... 

Another reaction that is characteristic of a-hydroxy aldehydes or ketones, which has been found of value for the characterisation of sugars, is the formation of osazones with phenylhydrazine. This reagent reacts with either an aldose... 

Over 200 different monosaccharides are known They can be grouped according to the number of carbon atoms they contain and whether they are polyhydroxy aide hydes or polyhydroxy ketones Monosaccharides that are polyhydroxy aldehydes are called aldoses, those that are polyhydroxy ketones are ketoses Aldoses and ketoses are further classified according to the number of carbon atoms m the mam chain Table 25 1 lists the terms applied to monosaccharides having four to eight carbon atoms... 

As shown for the aldotetroses an aldose belongs to the d or the l series accord mg to the configuration of the chirality center farthest removed from the aldehyde func tion Individual names such as erythrose and threose specify the particular arrangement of chirality centers within the molecule relative to each other Optical activities cannot be determined directly from the d and l prefixes As if furns ouf bofh d eryfhrose and D fhreose are levorofafory buf d glyceraldehyde is dexfrorofafory... 

Generating Haworth formulas to show stereochemistry m furanose forms of higher aldoses is slightly more complicated and requires an additional operation Furanose forms of D ribose are frequently encountered building blocks m biologically important organic molecules They result from hemiacetal formation between the aldehyde group and the C 4 hydroxyl... 

Up to this point all our attention has been directed toward aldoses carbohydrates hav ing an aldehyde function in their open chain form Aldoses are more common than ketoses and their role m biological processes has been more thoroughly studied Nev ertheless a large number of ketoses are known and several of them are pivotal inter mediates m carbohydrate biosynthesis and metabolism Examples of some ketoses include d nbulose l xylulose and d fructose... 

Aldoses are reducing sugars because they possess an aldehyde function m then-open chain form Ketoses are also reducing sugars Under the conditions of the test ketoses equilibrate with aldoses by way of enediol intermediates and the aldoses are oxidized by the reagent... 

Derivatives of aldoses in which the terminal aldehyde function is oxidized to a car boxylic acid are called aldonic acids Aldonic acids are named by replacing the ose ending of the aldose by omc acid Oxidation of aldoses with bromine is the most com monly used method for the preparation of aldonic acids and involves the furanose or pyranose form of the carbohydrate... 

The reaction of aldoses with nitric acid leads to the formation of aldaric acids by oxidation of both the aldehyde and the terminal primary alcohol function to carboxylic acid groups Aldaric acids are also known as saccharic acids and are named by substi tutmg aric acid for the ose ending of the corresponding carbohydrate... 

The presence of an aldehyde function m their open chain forms makes aldoses reactive toward nucleophilic addition of hydrogen cyanide Addition yields a mixture of diastereo meric cyanohydrins... 

The reaction is used for the chain extension of aldoses in the synthesis of new or unusual sugars In this case the starting material l arabinose is an abundant natural product and possesses the correct configurations at its three chirality centers for elaboration to the relatively rare l enantiomers of glucose and mannose After cyanohydrin formation the cyano groups are converted to aldehyde functions by hydrogenation m aqueous solution Under these conditions —C=N is reduced to —CH=NH and hydrolyzes rapidly to —CH=0 Use of a poisoned palladium on barium sulfate catalyst prevents further reduction to the alditols... 

Carbohydrates are polyhydroxy aldehydes and ketones Those derived from aldehydes are classified as aldoses, those derived from ketones are ketoses... 

Aldonic acid (Section 25 19) Carboxylic acid obtained by oxi dation of the aldehyde function of an aldose Aldose (Section 25 1) Carbohydrate that contains an aldehyde carbonyl group in its open chain form Alicyclic (Section 2 15) Term describing an a/iphatic cyclic structural unit... 

Ketose (Section 25 1) A carbohydrate that contains a ketone carbonyl group in its open chain form Kiliam-Fischer synthesis (Section 25 20) A synthetic method for carbohydrate chain extension The new carbon-carbon bond IS formed by converting an aldose to its cyanohydnn Reduction of the cyano group to an aldehyde function com pletes the synthesis... 

Oxidation to Sugar Acids and Lactones. When the aldehyde group of an aldose is oxidized, the resulting compound is an aldonic acid (salt form = aldonate) (11)4. Some aldonic acids are products of carbohydrate metaboHsm. 

Oxidation of the aldehyde group of an aldose to form a carboxyUc acid or carboxyUc acid anion is often used analytically to determine the amount of reducing sugar. The Benedict and Fehling methods measure the amount of reducing sugar present in a fluid. In these reactions, the oxidant, Cu ", is reduced to Cu". Cu" precipitates as CU2O, which can be measured in a variety of ways. In the ToUens test, Ag" is reduced to Ag. ... 

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