Carbohydrates

Definition:
Organic compounds composed of C, H and O with H
and O present in the same ratio as in water.
E.g. Glucose C6H12O6.

Exceptions:
Deoxy sugars such as Rhamnose C6H12O5, digitoxose
C6H12O4
Some non carbohydrates follow the definition:
Acetic acid C2H4O2
Formaldehyde HCHO
Lactic acid C3H6O3

New definition:

Optically active Polyhydroxy aldehydes or ketones, or

substances that hydrolyze to yield polyhydroxy
aldehydes or ketones.

Carbohydrates

Non-Sugars (Polysaccharides)

Sugars (Saccharides)

More than 10 sugar unites

Monosaccharides

Oligosaccharides
(3- 10 unites)

Disaccharides

Trioses e.g. Glyceraldehyde

Trisaccharides
e.g. Raffinose

Tetroses e.g. Erythose

Pentoses e.g. Arabinose
Hexoses

Reducing
Lactose
Maltose
Cellibiose

Non-Reducing
Sucrose

Tetrasaccharides

Pentasaccharides

Aldohexeoses
Glucose

Ketohexeoses
Fructose

Non-Sugars (Polysaccharides)
More than 10 sugar unites

Homopolysaccharides
Holosaccharides

Hexosanes

Glucosans
Starch
Glycogen
Cellulose
Dextrins

Heteropolysaccharides

Pentosans
Xylans

Fructosans
Inulin

Gums
Mucilages
Pectins
Agar
Heparin
Alginate

Physical Characters
Condition:
Sugars are white, crystalline in shape and with
sharp melting points, while polysaccharides are
white amorphous solids.

Taste:
Sugars have a sweet taste. Polysaccharides are
tasteless.

Solubility:
Monosaccharides are soluble in cold water and
hot alcohol. Polysaccharides are partially soluble
in hot water.

 Optical activity:

A compound is optically active when, in solution, it is capable to rotate

the plane of polarized light either to right (dextrorotatory, + or d) or to
the left (levorotatory, - or l).

Nickel prism

Plane polarized light

Normal light

The optical activity of a compound is measured by determination of its

specific optical rotation ([] Dt) using a polarimeter, and applying the
following equation:

[]D25 = /LC
Where: = extension of rotation,
L = length of tube (light path) in decimeter,
C = concentration g /ml,
25 = operating temperature (t) in 0C,
D = line spectrum of sodium light (589 nm).

Sugar isomers:
Hexoses like glucose have 4 asymmetric (chairal) carbons.
Number of isomers can be calculated from the formula:
Number of isomers = 2n
= 24 = 16

CHO
* CH OH
*
HO CH
* CH OH
* CH OH
CH2OH

D and L in sugars:
A monosaccharide in which the OH group attached to the carbon
atom next to the CH2OH (farthest asymmetric carbon atom from the
carbonyl group) is always to the right is designated as a D-sugar
and that with the same OH to the left as L -sugar.
D and L designations are like (R) and (S) designations in that they are not
necessarily related to the optical rotations of the sugars to which they are
applied. Thus, one may encounter sugars that are D (+) or D (-) and
others that are L (-) or L (+).

CHO
H

CHO
OH

CH2OH
D-Glyceraldehyde

HO

H
CH2OH

L-Glyceraldehyde

 - and - anomers of glucose:

When sugars under go cyclization C-1 became a new chairal
carbon and two isomers exist. They are called Anomers.
In the -anomer the OH group is directed downside and in the
-anomer is directed to the upper side.
These two forms have different specific rotation, in solution an
equlibrium exsit between the two forms (mutarotation
phenomenon).
H OH

H OH
H O

HO
HO

H
H

1 H

OH
OH

HO
HO

-glucopyranoside
Chair forms

H O
H
H

1 OH

OH
H

-glucopyranoside

CH2OH

CH2OH
H
OH

O
H

H
1

OH

OH
H

OH

-glucopyranoside

H
OH

OH

1
H

OH
H

OH

-glucopyranoside

Haworth formulations

 Mutarotation
When a sugar is dissolved in water, the specific rotation of
the solution gradually changes until it reaches to a
constant value due to equilibrium between the and
forms.
e.g. freshly prepared solution of -glucose has a specific
rotation +112o. When this solution is allowed to stand the
rotation falls till reach + 52.7o.
The equilibrium reached is:
36% D- glucose []D = + 18.7 0
64% D- glucose []D = + 112 0
The sum is + 52.7o

Terms used to describe isomerism:

Glucose and Galactose are different from each other in the
stereochemistry of carbon 4. They are described as Epimers.
Glucose and Mannose are different from each other in the
stereochemistry of carbon 2. They are described as Epimers.
Epimers:
CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

CHO
CH OH
HO CH
HO CH
CH OH
CH2OH
D-Galactose

CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

CHO
HO CH
HO CH
CH OH
CH OH
CH2OH
D- Mannose

 Galactose and Mannose are different from each other in

the stereochemistry of carbons 2 and 4. They are
described as DiastereoisomersDiastereomers.
Diastereomers:
CHO
CH OH
HO CH
HO CH
CH OH
CH2OH

CHO
HO CH
HO CH
CH OH
CH OH
CH2OH

D-Galactose

D- Mannose

 Glucose and Fructose have the same molecular

formula C6H12O6. They have different structures with
different function groups. They are described as
Structural Isomers.
Structural isomers:
CHO
CH OH
HO CH
CH OH
CH OH
CH2OH

CH2OH
CO
HO CH
CH OH
CH OH
CH2OH

D-Glucose

D-Fructose

Chemical Reaction Related to Colour

Tests for Carbohydrates
Effect of conc. acids:
Treatment with conc. mineral acid (HCl or H2SO4) leads to dehydration of
sugars and formation of the corresponding furfural.

Pentoses

CHO

Hexoses

HOH2C

CHO

Furfural
Volatile

5-Hydroxymethyl
furfural
less volatile

 Reaction of furfural with amines resulted in Shiffs bases with

different colours used as colour tests such as:

Molischs test:
Any carbohydrate + Alcoholic -naphthol then add conc. H2SO4 on
the wall of the test tube
Violet ring between the two layers.

Resorcinol test (for keto-hexoses):

Sugar solution + few crystals of Resorcinol + Equall volume of conc.
HCl and warm on water bath
Rose Red Colour.

Furfural test (Differentiate between Pentoses and Hexoses):

Pentose + Coc. Acid and heat, expose the vapours to Aniline
acetate paper
Red colour
Hexoses give negative result.

Effect of Alkalis
Strong alkalis:
Polymerization.

Weak alkalis:
Isomerization.
H
C=O
CH OH
HO CH
CH OH
CH OH
CH2OH

CHOH
C OH
HO CH
CH OH
CH OH
CH2OH

D-Glucose

CH2OH
C=O
HO CH
CH OH
CH OH
CH2OH
D-Fructose

CHO
HO CH
HO CH
CH OH
CH OH
CH2OH
D- Mannose

Oxidation
Mild Oxidation:
These are oxidizing agents like Bromine water that convert the CHO
group to COOH to produce onic acids.
Colour tests based on this reaction:
Fehlings reduction test:
Sugar solutions + Fehlings A (CuSO4) + Fehlings B (NaOH, NaK tartarate
rochell salt), heat on water bath
Red Precipitate

RCHO + Cu++

CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

RCOOH + Cu2O

I2 or Fehling's

COOH
CH OH
HO CH
CH OH
CH OH
CH2OH
Gluconic acid

Barfoeds test:
Sugar solution + Barfoeds reagent (Cu Acetate/Acetic acid),
heat for 3 minutes on boiling water bath
Red ppt with
monosaccharides only.
Acidic medium decreases the oxidation power of Cu++.

Strong Oxidation
These are oxidizing agents like HNO3 that convert the CHO
and CH2OH group to COOH to produce aric acids.
CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

HNO3

COOH
CH OH
HO CH
CH OH
CH OH
COOH
Saccharic acid

 Glalactaric acid (Mucic acid) test:

Oxidation of galactose resulted in the formation of
Galactaric acid. It is a meso compound insoluble in water
and have zero optical rotation.

CHO
CH OH
HO CH
HO CH
CH OH
CH2OH
D-Galactose

HNO3

COOH
CH OH
HO CH
HO CH
CH OH
COOH
Galactaric acid

Enzymatic oxidation
Takes place in plants and resulted in the oxidation of the
primary alcohol group only producing uronic acids.
CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

CHO
CH OH
HO CH
CH OH
CH OH
COOH
Glucuronic acid

COOH
H H
OH OH
H

O
OH
H H
OH

Reduction
This resulted in the reduction of the CHO to CH 2OH
producing Sugar Alcohols. Sodium borohydride
or H2/Pt are examples of reducing agents.
Glucose
Galactose
Mannose

CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

Sorbitol
Dulcitol
Mannitol

CH2OH
CH OH
HO CH
CH OH
CH OH
CH2OH
Sorbitol

Examples:

Pentoses

-D-Ribose: found in all plant and animal cells as the carbohydrate part of
nucleic acids e.g. ribonucleic acid (RNA).
-D-Xylose (or wood sugar): prepared from corncobs, bran, straw (or any woody
material) by boiling with acids, fermenting out any glucose present with yeast,
and crystallizing the D-xylose from the evaporated solution.
-L-Arabinose (or pectin sugar): found in gums, pectic substances,
accompanying hemicelluloses and forms the sugar part of several glycosides.
CHO

CHO

CHO

CH OH

CH OH

CH OH

HO CH

CH OH

HO CH

CH OH

CH OH

CH2OH

CH2OH

CH2OH
L-Arabinose

D-Ribose

HO CH

D-Xylose

Hexoses
1- -D-Glucose
(dextrose, grape sugar, blood sugar or cornmon sugar)
Occurrence:
Widely distributed in nature. Present in Grape and blood.

Preparation:
D-Glucose is commercially prepared from starch by:
Autoclaving (at 150 0C) an aqueous starch suspension (15-20%) with dilute
acid (0.03 N hydrochloric acid) for 30 minutes (complete hydrolysis).
CHO
CH OH
HO CH
CH OH
CH OH
CH2OH
D-Glucose

CH2OH
O OH
H H
OH H H
OH
H
OH
D-Glucopyranose

 Uses:
As source of energy either by mouth or IV injection.
IV solutions to restore blood volume.
Shocks following insulin administration.
As osmotic diuretic.
Sweetening agent for Pharmaceutical preparations, ice-cream
and candy.

Liquid glucose:
Preparation:
It is prepared by partial acid hydrolysis of starch using dilute
hydrochloric acid and heating for 20 minutes at about 30
pounds pressure.

Composition:
It consists of a mixture of glucose, dextrin, maltose and water.

Uses:
Used as sweetening agent, as substitute for sucrose and as an
excipient in massing pills.

2- Fructose
(Levulose, Fruit Sugar)
Preparation:
Acid hydrolysis of Inulin.
Hydrolysis of Sucrose.

Sucrose

Acid or Enzyme

Fructose + Glucose
Ca(OH)2

Ca fructosate
ppt

Ca glucosate
Solution

CH2OH
C O
HO CH
CH OH
CH OH
CH2OH
D-(-)-Fructose

Uses:
Infant food.
Diabetic food.
Diet control.

HOH2C

OH

HO CH2OH
OH
OH
-D-(-)-Fructofuranose

Some Monosaccharide derivatives in

Pharmacy and Medicine
Gluconic acid and its salts:
Preparation:
Gluconic acid is prepared from glucose by mild oxidation using either
dilute HNO3 or Br2/Na2CO3 or Electrically or by fermentation using
Acetobacter aceti.

Uses:
Ca gluconate is used (by i.v. or orally) for treatment calcium
deficiency.
Ferrous gluconate, (orally or by i.v.) is used in iron deficiency.

These salts are characterized by being more easily adsorbed

than other Ca or Fe salts.

 Glucuronic Acid:
Naturally present in Gums and Mucilage's. It can be prepared by
Enzymatic oxidation of glucose.
Uses:
Treatment of certain arthritic condition as it is a component of
cartilages, joint capsules and fluids, nerve sheath and tendons.

Aurothioglucose:
Treatment of rheumatic arthritis by IM injection.

CH2OH
O
H H
H
OH
OH
H

H S

Au

OH

Aurothioglucose

 Auranofin:
It is the alkyl Phosphine Gold complex with Acetylated thioglucose.
Treatment of rheumatic arthritis orally.
CH2OR
O S
H H

OR

Sorbitol and Mannitol:

Preparation:

OR

H H

OR

Au P(C2H5)3

R= COCH3

Auranofin

Sorbitol is prepared by reduction of glucose and mannitol by reduction of mannose.

Uses:
Sorbitol is used as a mild laxative, in preparation of spans and tweens,
sweetening agent, osmotic diuretic and in some food and cosmetics
industries.
Mannitol is used as an osmotic diuretic, laxative, , vasodilator (mannitol
hexanitrate), antineoplastic (mannitol- (mannitol hexanitrate). nitrogen
mustard) and in laboratory diagnosis of kidney function.