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Predict the products obtained when D-galactose reacts with each reagent.

(a) Br2 and H2O

(b) NaOH,H2O

(c)CH3OH, H+

(d) Ag(NH3)+2OH+

(e) H2, Ni

(f) excess Ac2O and pyridine

(g) excess CH3I ,Ag2O

(h) NaBH4

(i) Br2 , H2O then H2O2 and Fe2(SO4)3

(j) (1) KCN/HCN; (2) H2 Pd/BaSO4; (3) H3O+

(k)excess HIO4

Short Answer

Expert verified

a)

b)

c)

d)

e)

f)

g)

h)

i)

j)

k)

Step by step solution

01

Bromine water oxidation of monosaccharides

Bromine water oxidises aldehyde group ( -CHO) of an aldose into carboxylic acid (-COOH) . Moreover, bromine water does not oxidize alcohols and ketoses. The product formed from bromine water oxidation is known as an aldonic acid.

02

Formation of glycosides

Aldehydes and ketones can be converted to acetals when they are treated with an alcohol and a small amount of an acid catalyst. Under these conditions, aldoses and ketoses can also be converted to acetals which are known as glycosides

03

Ester formation

The hydroxy (-0H) groups of a sugar can be converted to acetate esters by the treatment with acetic anhydride and pyridine. The stereochemistry is usually retained at the anomeric carbon.

04

 Step 4: Formation of methyl ether

Hydroxy groups of sugar can be converted to methyl ethers by treating with methyl iodide (CH3I) and silver oxide (Ag2O). CH3-I group can be polarised by silver oxide (Ag2O) , which makes the methyl carbon more strongly electrophilic. Attack by the -OH group of carbohydrate is then followed by deprotonation which gives the ether.

05

 Step 5: Reduction of monosaccharide

Aldoses and ketoses can be reduced to their corresponding polyalcohols, known as sugar alcohols or alditols by using the reagents such as sodium borohydride (NaBH4) or by catalytic hydrogenation using a nickel (Ni) catalyst.

06

Ruff degradation (shortening of the carbon chain)

Synthesis of new sugars and its structure can be known by a process known as Ruff degradation. The sugar chains are shortened in Ruff degradation. It is a two- step process which is given as below:

(!) oxidation of aldose to aldonoic acid by bromine water (Br2/H2O) .

(2)aldonic acid formed is treated with hydrogen peroxide (H2O2) and ferric sulfate, Fe2(SO4)3 that oxidises the carboxyl group to carbon dioxide (CO2) and the resulting aldose is formed with one fewer carbon atom.

07

Step 7:Kiliani- Fischer synthesis (lengthening of the carbon chain)

Adding one carbon atom to the aldehyde end of the aldose lengthens an aldose chain. The sugar chain is lengthened as a result of this process with a new carbon atom at C1 position and the aldehyde group (C1 position earlier) is now moved to C2 position. For determining the structure of existing sugars and also for synthesizing new sugars, Kiliani-Fischer synthesis is used.

08

 Step 8: Prediction of the products

(a)Bromine water oxidation of D-galactose gives galactonic acid.

b)

c)

(d) An aldose in its open chain form has an aldehyde group which reacts with Tollen鈥檚 reagent to yield an aldonic acid a silver mirror.

(e)Aldoses are reduced to its corresponding polyalcohols, known as alditols by H2Ni .

f)

g)

(h)Aldoses are reduced to its corresponding polyalcohols, known as alditols by NaBH4.

i)

j)

k) D- galactose when treated with HI O4 gives formic acid and formaldehyde.

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Most popular questions from this chapter

Draw the structures (using chair conformations of pyranoses) of the following disaccharides.

(a) 4-O-( -D-glucopyranosyl)-D-galactopyranose

(b) -D-fructofuranosyl-尾 -D-mannopyranoside

(c) 6-O-(尾 -D-galactopyranosyl)-D-glucopyranose

Some protecting groups can block two OH groups of a carbohydrate at the same time. One such group is shown here, protecting the 4-OH and 6-OH groups of 尾 -D-glucose.

(a) What type of functional group is involved in this blocking group?

(b) What did glucose react with to form this protected compound?

(c) When this blocking group is added to glucose, a new chiral center is formed. Where is it? Draw the stereoisomer that has the other configuration at this chiral center. What is the relationship between these two stereoisomers of the protected compound?

(d) Which of the two stereoisomers in part (c) do you expect to be the major product? Why?

(e) A similar protecting group, called an acetonide, can block reaction at the 2鈥 and 3鈥 oxygens of a ribonucleoside. This protected derivative is formed by the reaction of the nucleoside with acetone under acid catalysis. From this information, draw the protected product formed by the reaction.

After a series of Kiliani鈥揊ischer syntheses on (+)-glyceraldehyde, an unknown sugar is isolated from the reaction mixture. The following experimental information is obtained:

(1) Molecular formula C6H12O6

(2) Undergoes mutarotation.

(3) Reacts with bromine water to give an aldonic acid.

(4) Reacts with HNO3 to give an optically active aldaric acid.

(5) Ruff degradation followed by HNO3 oxidation gives an optically inactive aldaric acid. (6) Two Ruff degradations followed by HNO3 oxidation give meso-tartaric acid.

(7) When the original sugar is treated with CH3I and Ag2O, a pentamethyl derivative is formed. Hydrolysis gives a tetramethyl derivative with a free hydroxy group on C5.

(a) Draw a Fischer projection for the open-chain form of this unknown sugar. Use Figure 23-3 to name the sugar.

(b) Draw the most stable conform

The relative configurations of the stereoisomers of tartaric acid were established by the following synthesis:

(1) D-(+)-glyceraldehydediastereomers A and B (separated)

(2) Hydrolysis of A and B using aqueous Ba(OH)2 gave C and D, respectively.

(3) HNO3 oxidation of C and D gave (-)-tartaric acid and meso-tartaric acid, respectively.

(a) You know the absolute configuration of D-(+)-glyceraldehyde, Use Fischer projections to show the absolute configurations of products A, B, C, and D.

(b) Show the absolute configurations of the three stereoisomers of tartaric acid: (+)-tartaric acid, (-)-tartaric acid, and meso-tartaric acid.

a) Draw D-allose, the C3 epimer of glucose.

b) Draw D-talose, the C2 epimer of D-galactose.

c) Draw D-idose, the C3 epimer of D-talose. Now compare your answers with Figure 23-3.

d) Draw the C4 鈥渆pimer鈥 of D-xylose. Notice that this 鈥渆pimer鈥 is actually an L-series sugar, and we have seen its enantiomer. Give the correct name for this L-series sugar.

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