Module 11 Carbohydrates

Lecture 29 Carbohydrates I

11.1 Introduction
Carbohydrates are polyhydroxy aldehydes or ketones. They are primarily produced by
plants and form a very large group of naturally occurring organic substances. Some
common examples are cane sugar, glucose, starch, etc. They have general molecular
formulas that make them appear to be hydrates of carbon, C
n(H2O)n, from where the

name carbohydrate was derived. Carbohydrates are formed in the plants by

photosynthesis from carbon dioxide and water in the presence of sunlight (Scheme 1).
Oxidation
C6H12O6 + 6O2 6CO2 + 6H2O + Energy
Photosynthesis
Glucose

Scheme 1

11.2 Classification
Carbohydrates are classified into two main classes, sugars and polysaccharides.
11.2.1 Sugars
Sugars are sweet crystalline substances that are soluble in water. These are further
classified on the basis of their behavior on hydrolysis.
 11.2.1.1 Monosaccharides
The simplest form of carbohydrates is the monosaccharide. 'Mono' means 'one' and
'saccharide' means 'sugar'. Monosaccharides are polyhydroxy aldehyde or ketone that
cannot be hydrolyzed further to give simpler sugar. They may again be classified on the
basis of the nature of carbonyl group.
• Polyhydroxy aldehydes are called aldoses. Example: Glucose

• Polyhydroxy ketones are called ketoses. Example: Fructose

1 1
HC O CH2OH
2 2
H OH C O
3 3
HO H HO H
4 4
H OH H OH
5 5
H OH H OH
6 6
CH2OH CH2OH

Glucose Fructose
(Aldose) (Ketose)

The aldoses and ketoses are further divided based on the number of carbons present in
their molecules, as trioses, tetroses, pentoses, hexoses etc. They are referred to as
aldotrioses, aldotetroses, aldopentoses, aldohexoses, ketohexoses etc.

Number of Carbons General term Aldehyde Ketone

3 Triose Aldotriose Ketotriose
4 Tetrose Aldotetrose Ketotetrose
5 Pentose Aldopentose Ketopentose
6 Hexose Aldohexose Ketohexose
7 Heptose Aldoheptose Ketoheptose
11.2.1.2 Oligosaccharides
Carbohydrates that produce two to ten monosaccharide units during the hydrolysis are
called oligosaccharides. They can be further classified based on the number of
monosaccharide units formed on hydrolysis.
Disaccharides:
They give two monosaccharide units on hydrolysis, which may be the
same or different. For example, sucrose on hydrolysis gives one molecule each of glucose
and fructose, whereas maltose gives two molecules of glucose (Scheme 1).
C12H22O11 + H2O C6H12O6 + C6H12O6
sucrose glucose f ructose

C12H22O11 + H2O 2 C6H12O6

maltose glucose
Scheme 1

Trisaccharides:
These carbohydrates yield three molecules of monosaccharides units on
hydrolysis (Scheme 2).
C18H32O16 + 2 H2O C6H12O6 + C6H12O6 + C6H12O6
raffinose glucose f ructose galactose

Scheme 3

11.2.1.3 Polysaccharides
These carbohydrates give a large number of monosaccharide units on hydrolysis. These
monosaccharide units are joined together by oxide bridges. These linkages are called
glycosidic linkages. The common and widely distributed polysaccharides correspond to
the general formula (C 6H10O5)n. Polysaccharides are not sweet in taste, so they are called
non-sugars. Some common examples are starch, cellulose, glycogen, etc (Scheme 3).
+
H
(C6H10O5)n + n H2O n C6H12O6
starch glucose

Scheme 3
11.3 The D and L Notations
The notations D and L are used to describe the configurations of carbohydrates and
amino acids. Glyceraldehyde has been chosen as arbitrary standard for the D and L
notation in sugar chemistry. Because, this has an asymmetric carbon and can exist as a
pair of enantiomers.
O HC O HC O
H OH HO H
HO H
OH CH2OH CH2OH

erra
glycce alde e
ehyde D--glycce
erra
alde
ehyde
e L--glycce
erra
alde
ehyde
e

In a Fischer projection, the carbonyl group is always placed on the top position for
monosaccharide. From its structure, if the –OH group attached to the bottom-most
asymmetric center (the carbon that is second from the bottom) is on the right, then, the
compound is a D-sugar. If the –OH group is on the left, then, the compound is a L-sugar.
Almost all sugars found in nature are D-sugar.

HC O HC O
H OH HO H
HO H H OH
H OH HO H
H OH HO H
CH2OH CH2OH
D-series L-series
(D-glucose) ( -glucose)
L

Like R and S, D and L indicate the configuration of an asymmetric carbon, but they do
not indicate whether the compound rotates polarized light to the right or to the left. For
example, D-glyceraldehyde is dextrorotatory, whereas D-lactic acid is levorotatory. In
other words, optical rotation, like melting or boiling points, is a physical property of a
compound, whereas “ R, S, D, and L” are conventions humans use to indicate the
configuration of a molecule.

HC O COOH
H OH H OH
CH2OH CH3

D-(+)-glyceraldehyde D-(-)-lactic acid

11.3.1 Configuration of the Aldoses
Aldotetrose
The: structural formula of aldotetrose is CH 2OH·CHOH·CHOH·CHO. There
are four stereoisomers (two pairs of enantiomers). Those stereoisomers correspond to D-
and L-erythrose and D- and L-threose.
HC O HC O HC O HC O
H OH HO H HO H H OH
H OH HO H H OH HO H
CH2OH CH2OH CH2OH CH2OH

D-erythrose L-erythrose D-threose L-threose

Aldopentose: The structural formula of aldopentose is

CH2OH·CHOH·CHOH·CHOH·CHO. Since it contains three asymmetric carbons and
there are eight stereoisomers (four pairs of enantiomers) possible. Those are the D- and
L-forms of ribose, arabinose, xylose and lyxose.