Bindura University of Science Education

Faculty of Science
Chemistry
Bindura, Zimbabwe.
Assignment
BSc Chemistry CH 303- December/Jan block 2015
Total Marks 30
Due date: 04/01/2016

Answer the following questions

BHEBE NKWANELE B1441641 2.1
1. What are monosaccharides, disaccharides, and polysaccharides and give one example
For each saccharides?
Monosaccharides - simple sugars with multiple OH groups. Based on number of carbons
(3, 4, 5, 6), a monosaccharide is a triose, tetrose, pentose or hexose.
Disaccharides - 2 monosaccharides covalently linked, example is maltose

Polysaccharides - polymers consisting of chains of monosaccharide or disaccharide units

starch is an example.

2. Explain the formation of hemiacetal and ketal?

An aldehyde reacts with alcohol to form hemiacetal
A ketone reacts with alcohol to for hemiketal
H
C

R'

OH

R'

OH

aldehyde

alcohol

hemiacetal

R
C

R
O

"R

OH

R'

ketone

"R

C
R'

alcohol

hemiketal

OH

3.

Explain the howarth projections of pentoses and hexoses?

[M 5]

D-glucose forms a hexoses intramolecular hemiacetal as the C1 aldehyde and C5 OH

reacts to form a six member pyranose ring.
Hexoses eg D-glucose

Therefore, the CH2OH group will be pointing up in the Haworth projection.

Moreover, theOH
group on the C-2 will be pointing down and its H substituent will be pointing
up. And, the
OH group on the C-3 will be pointing up while its H substituent points
down, and so on.
In the next step, the carbonyl oxygen becomes protonated and singly
bonded to C-1. The OH group on C-5 becomes deprotonated and forms an
O-C bond with C-1, resulting in a sixmembered ring

In -D-glucose the anomeric carbons OH group is on the left. In the Haworth

projection this
alcohol group points up. The other substituents point up in the Haworth
projection if they are on
the left side in the Fischer projection, and point down if they are on the right
side in the Fischer Projection
In -D-glucose the anomeric carbons OH group is on the right. In the
Haworth projection of
-D-glucose illustrated above the OH group points down. Once again, the
rest of the
substituents also follow the translation rule from Fischer to Haworth.

4. What is mutarotation. Discuss the mutarotation of d-glucose

[M 6]

mutarotation
CH 2OH
O

HO
HO
HO

-D-glucose

CH 2OH
OH

HO
HO

OH

HO
OH

m.p. 146C, = +112

HO
O

open-chain form

CH 2OH
O

HO
HO

-D-glucose
m.p. 150C, = +19

When -D-(+)-glucose is dissolved in wate

r, the specific rotation of
the sample decreases from a value of +112 to a value of +53. The specific
rotation of 112 corresponds to -D-(+)-glucose. The specific rotation of
+53 corresponds to an equilibrium mixture of -D-(+)-glucose and -D-(+)glucose. A change in the optical rotation of freshly prepared solutions of
sugars is called mutarotation. The forms of glucose involved in mutarotation
are the open chain form and two cyclic forms, which are in equilibrium. The
2 cyclic forms are diastereomers, which have different physical properties
(different m.p. and specific rotations). They are referred to as anomers since
they differ only in the configuration at the hemiacetal carbon. If either cyclic
compound is dissolved in water, the specific rotation changes to +53. The

specific rotation decreases from +112 to +53 when -D-(+)-glucose is

dissolved in water and increases from +19 to +53 when -D-(+)-glucose is
dissolved in water. The mutarotation of glucose is acid-catalyzed and
proceeds rapidly at a pH of 7.

5. Write note on the following:

a. Ruff degradation

[M 10]

Is a two step process where the aldose is oxidized to its aldonic acid by treatment with
bromine water.The is followed by the treatment of hydrogen peroxide and ferricsulphate
which oxidises the carboxyl group to carbondioxide,and gives a shorter aldose with one
carbon less new sugar. This is used to determine the structure and synthesis of new sugars

Chain Shortening
1.

b. Reduction
Reduction of cyanohydrins by hydrogenation results in the two imines which are
hydrolyzed to sugars by using a poisoned catalyst on barium sulfate to avoid over
hydrogenation/over reduction.

Sodium borohydride reduction of an aldose makes the ends of the resulting alditol chain
identical, HOCH2(CHOH)nCH2OH, thereby accomplishing the same configurational change
produced by oxidation to an aldaric acid. Thus, allitol and galactitol from reduction of allose and
galactose are achiral, and altrose and talose are reduced to the same chiral alditol. A summary of
these redox reactions, and derivative nomenclature is given in the following table.
Derivatives of HOCH2(CHOH)nCHO
HOBr Oxidation

>

HOCH2(CHOH)nCO2H
an Aldonic Acid

HNO3 Oxidation

>

H2OC(CHOH)nCO2H

an Aldaric Acid
NaBH4 Reduction

>

HOCH2(CHOH)nCH2OH
an Alditol

Osazone Formation
1.

2.

The osazone reaction is used to identify aldose sugars differing in configuration only at the
alpha-carbon. The equation 1 shows the general form of the osazone reaction, which effects an
alpha-carbon oxidation with formation of a bis-phenylhydrazone, known as an osazone.
Application of the osazone reaction to D-glucose and D-mannose demonstrates that these
compounds differ in configuration only at C-2.
C. Oxidation of sugars.
Monosaccharides are oxidized by a variety of reagents. The aldehyde group of an
aldose is easily oxidized.
Some oxidants selectively oxidizes the terminal alcohol group. While strong
oxidizing agents like nitric acid oxidizes both the aldehyde end and the alcohol
terminal.
Oxidation can be used to determine functional groups of the sugars, and also can be
used to determine the stereochemistry and as a part to synthesis to convert one sugar
to the other.

Oxidation with Br2 of -d-glucose and -d-glucose

The ribose oxidation is shown in equation 2 below.

1.
2.

3.

Other aldose sugars may give identical chiral aldaric acid products, implying a unique
configurational relationship. The examples of arabinose and lyxose shown in equation 3 above
illustrate this result. A Fischer projection formula may be rotated by 180 in the plane of
projection without changing its configuration

Tollen reducing agent: Test for the reducing sugars

For example oxidation can be used to identify glucose from galactose.One of the sugar gives an
optically active alderic acid while the other gives any non-active alderic acid