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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

(a) Which of the D-aldopentoses will give optically active aldaric acids on oxidation with HNO3 ?

(b) Which of the D-aldotetroses will give optically active aldaric acids on oxidation withHNO3 ?

(c) Sugar X is known to be a D-aldohexose. On oxidation with HNO3 , X gives an optically inactive aldaric acid. When X is degraded to an aldopentose, oxidation of the aldopentose gives an optically active aldaric acid. Determine the structure of X.

(d) Even though sugar X gives an optically inactive aldaric acid, the pentose formed by degradation gives an optically active aldaric acid. Does this finding contradict the principle that optically inactive reagents cannot form optically active products?

(e) Show what products results if the aldopentose formed from degradation of X is further degraded to an aldotetrose. DoesHNO3 oxidize this aldotetrose to an optically active aldaric acid?

Which of the following sugars are reducing sugars? Comment on the common name sucrose for table sugar.

(a) methylDgalactopyranoside (b) Lidopyranose (an aldohexose)

(c) Dallopyranose (d) Lribofuranoside

(e) (f)

Trehalose is a nonreducing disaccharide (C12H22O11) isolated from the poisonous mushroom Amanita muscaria. Treatment with an 伪 -glucosidase converts trehalose to two molecules of glucose, but no reaction occurs when trehalose is treated with a 尾 -glucosidase. When trehalose is methylated by dimethyl sulfate in mild base and then hydrolyzed, the only product is 2,3,4,6-tetra-O-methylglucose. Propose a complete structure and systematic name for trehalose.

Draw the following sugar derivatives.

  1. ethyl--D-glucopyranoside
  2. 2,3,4,6-tetra-O-ethyl-D-mannopyranose
  3. 1,3,6-tri-O-ethyl-D-fructofuranose
  4. Ethyl-2,3,4,6-tetra-O-methyl--D-galactopyranoside

Draw the structures of the compounds named in Problem 23-20 parts (a), (c), and (d). Allose is the C3 epimer of glucose and ribose is the C2 epimer of arabinose.

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