Pharmacognosy- 1

PHG 222

Prof. Dr. Amani S. Awaad

Professor of Pharmacognosy
Pharmacognosy Department,
College of Pharmacy Salman Bin Abdulaziz
University,
Al-Kharj. KSA.
Email: amaniawaad@hotmail.com
Carbohydrates
To know what is carbohydrates
To Recognize Classification of
carbohydrates
To Identify types Monosaccharides
To know Structural formulas for
Monosaccharides
To understand Reactions of
Monosaccharides
To know Polysaccharides
To understand and identefiy Carbohydrate
Antibiotics
 Carbohydrates

• Carbohydrates [CX(H2O)Y] are usually

defined as polyhydroxy aldehydes and
ketones or substances that hydrolyze to
yield polyhydroxy aldehydes and ketones.

• Simple carbohydrates are known as

sugars or saccharides (Latin saccharum,
sugar) and the ending of the names of
most sugars is –ose. For example:

1. Glucose (for the principle sugar in blood)

2. Fructose (for a sugar in fruits and honey)
3. Sucrose (for ordinary table sugar)
4. Maltose (for malt sugar)
 Carbohydrates

Classification of carbohydrates
• Monosaccharide (C6H12O6)
it is a simple carbohydrate, one that one attempted hydrolysis is not cleaved to smaller
carbohydrates. e.g. glucose
• Disaccharide on hydrolysis is cleaved to two monosaccharide, which may be the same
or different. e.g. sucrose
• Oligosaccharide (oligos is a Greek word that means “few”) yields 3 10
monosaccharide unit on hydrolysis. e.g. raffinose
• Polysaccharides are hydrolyzed to more than 10 monosaccharide units. Cellulose is a
polysaccharide molecule that gives thousands of glucose molecules when completely
hydrolyzed.
 Carbohydrates

Classification of carbohydrates

Monosaccharaides

• Over 200 different monosaccharides

are known.
• Monosaccharides are classified
according to:
1. The number of carbon atoms present
in the molecule.
2. Whether they contain an aldehyde or
ketone group.
• A monosaccharide containing three
carbon atoms is called a triose; one
containing four carbon atoms is called
a tetrose.
• A monosaccharide containing an
aldehyde group is called an aldose;
one containing a keto group is called a
ketose.
 Carbohydrates

Classification of carbohydrates

Monosaccharaides
• The simplest monosaccharide is
glyceraldehyde, which contains a
stereocenter. Therefore, it exist in two
enantiomeric forms.

• In 1906, (+)-glyceraldehyde is designated

D-(+)- glyceraldehyde
• and ()- glyceraldehyde is designated L-
()- glyceraldehyde.

• These two compounds serve as

configurational standards for all
monosaccharides.
 Carbohydrates

Classification of carbohydrates
Monosaccharaides
• A monosaccharide whose highest
numbered stereocenter (the
penultimate carbon) has the same
configuration as D-(+)-
glyceraldehyde is designated as a D
sugar; one whose highest numbered
stereocenter has the same
configuration as L-()-
glyceraldehyde is designated as an L
sugar.
• D and L designations are not related
to the optical rotations of the sugars
to which they are applied.
• One may encounter other sugars that
are D-(+)- or D-()- and ones that are
L-(+)- or L-()-.
 Carbohydrates
Monosaccharaides
Structural formulas for Monosaccharides

• Fisher projection
• Haworth formulas O
Pyran
•  anomer or  anome
O
Not all carbohydrates exist in Furan

equilibrium with six-membered

hemiacetal rings, in several instances the
ring is five membered.

If the monosaccharide ring is six

membered, the compound is called a
pyranose (e.g.  -D-glucopyranose );

if the ring is five membered, the

compound is designated as a furanose.
(e.g.  -D-ribofuranose).
 Carbohydrates
Monosaccharaides
Structural formulas for Monosaccharides
Mutarotation
H2O H2O
• The spontaneous change that takes
place in the optical rotation of  and
 anomers of a sugar when they are
dissolved in water. The optical
rotations of the sugars change until
they reach the same value.
• the explanation for this mutarotation
lies in the existence of an equilibrium
between the open-chain form of D-
(+)-glucose and the  and  forms of
the cyclic hemiacetals.
• the concentration of open-chain D-
(+)-glucose in solution at equilibrium
is very small.
 Carbohydrates
Monosaccharaides
Structural formulas for Monosaccharides

Glycoside Formation
Hemiacetal: a functional group, consisting of a carbon atom bonded to an alkoxy group
and to a hydroxyl group. Hemiacetals are synthesized by adding one molar equivalent of
an alcohol to an aldehyde or a ketone.
The reactions of aldehydes and ketones with alcohols parallel their reactions
with water.
 Carbohydrates
Monosaccharaides
Structural formulas for Monosaccharides
Glycoside Formation
• Carbohydrate acetals,
generally, are called
glycosides, and an acetal of
glucose is called a glucoside.
• The methyl D-glucosides have
been shown to have six-
membered ring, so they are
properly named methyl -D-
glucopyranoside and -D-
glucopyranoside.
• Glycosides are stable in basic
solutions because they are
acetals.
• In acidic solutions, glycosides
undergo hydrolysis to produce
a sugar and an alcohol
(aglycone).
 Carbohydrates
Sugars that contain nitrogen
1. Glycosylamines
Glycosylamines are a class of biochemical compounds
consisting of an amine with a β-N-glycosidic bond to a
carbohydrate, forming a cyclic hemiaminal ether bond
(α-aminoether).
Adenosine is an example of a glycosylamine that is
also called a nucleoside.

2. Amino sugars
A sugar in which an amino group replaces a
nonanomeric OH group. e.g. D-glucosamine.
•D-glucosamine can be obtained by hydrolysis
of chitin, a polysaccharide found in the shells of
lobsters and crabs and in the external skeletons
of insects and spiders.

Glucosamine (C6H13NO5) is an amino sugar and a prominent precursor in the

biochemical synthesis of glycosylated proteins and lipids.
 Carbohydrates
Reactions of Monosaccharides
1. Enolization, Tautomerization, and Isomerization
OH

Dissolving monosaccharides in aqueous base RC CR2

Enol
causes them to undergo enolizations and a
O O
series of keto-enol tautomerizations that lead to
RC CR2 RC CR2
isomerizations.
Enolate ion

Enols are in equilibrium with an isomeric

aldehyde or ketone, but are normally much less
stable than aldehydes and ketones.
Enolate ion is the conjugate base of an enol.
Enolate ions are stabilized by electron
delocalization.
Tautomerizm is a process by which two
isomers are interconverted by a movement of
an atom or a group. Enolization is a form of
tautomerism
Tautomerization creates structural isomers
D-Glucose to D- Fructose
Note: Formation of a glycoside prevents enolization
 Carbohydrates
Reactions of Monosaccharides

2. Formation of Ethers
The hydroxyl groups of
monosaccharides are more acidic than
those of ordinary alcohols because the
monosaccharide contains so many
electronegative oxygen atoms, all of
which exert electron-withdrawing
inductive effects on nearby hydroxyl
groups.
In aqueous NaOH, the hydroxyl
groups are converted to alkoxide ions
and each of these in turn, reacts with
dimethyl sulfate to yield a methyl
ether.

Formation of Ethers
– Exhaustive Methylation
• SN2 Mechanism
• Base-catalyzed
 Carbohydrates
Reactions of Monosaccharides

3. Conversion to Esters

Treating a monosaccharide with excess acetic anhydride and a weak base

(such as pyridine or sodium acetate) converts all of the hydroxyl groups,
including the anomeric hydroxyl, to ester groups

H OH H OCCH3
O
H O H O
HO (CH3CO)2O H3CCO
HO Pyridine, 0°C H3CCO
H H
OH OH OCCH3 OCCH3
H O H
O O
 Carbohydrates
Reactions of Monosaccharides

4. Oxidation Reactions of Monosaccharides

A. Fehling’s solution or Benedict’s reagent
A characteristic property of an aldehyde
function is its sensitivity to oxidation.
Carbohydrates that give positive tests with
Fehling’s or Benedict’s reagents are termed Benedict’s
Reducing Sugars.
Ketoses are also reducing sugars, since under
the conditions of the test, ketoses
equilibrate with aldoses by way of enediol
intermediates, and the aldoses are oxidized
by the reagents Fehling’s

O O
R CH 2Cu2+ 5HO R CO Cu2O 3H2O

Aldehyde From copper(II) Hydroxide Carboxylate Copper(I) Water

sulfate ion anion oxide
 Carbohydrates
Reactions of Monosaccharides

4. Oxidation Reactions of Monosaccharides

B. Bromine Water: the synthesis of aldonic acids

Bromine water is a general reagent

that selectively oxidizes the - CHO
group to α-CO2H group

Bromine Water:
The Synthesis of Aldonic Acid
Selectively oxidizes Aldehydes,
Gives a positive Test for Aldose,
and
Gives a negative test for Ketose.
 Carbohydrates
Reactions of Monosaccharides
4. Oxidation Reactions of Monosaccharides
C. Nitric Acid Oxidation: Aldaric Acids CHO CO2H
Dilute nitric acid – a stronger oxidizing agent
than bromine water – oxidizes both the –CHO HNO3
(CHOH)n (CHOH)n
group and the terminal –CH2OH group of an
aldose to –CO2H group. These dicarboxylic
acids are known as aldaric acids. CH2OH CO2H

Aldose Aldaric acid

 Carbohydrates
Reactions of Monosaccharides
4. Oxidation Reactions of Monosaccharides
D. Periodate oxidations: oxidative cleavage of polyhydroxy compounds
Compounds that have hydroxyl groups on adjacent atoms undergo O

C OH
oxidative cleavage when they are treated with aqueous periodic acid HIO4 2 C HIO4 H2O
C OH
(HIO4).
In these periodate oxidations that for every C-C bond broken, a C-O
bond is formed at each carbon.

When three or more –CHOH groups are contiguous,

the internal ones are obtained as formic acid. For
example, glycerol

Stoichiometric cleavage
Oxidative cleavage also takes place when an –OH
group is adjacent to the carbonyl group of an
aldehyde or ketone (but not that of an acid or an
ester). For example, glyceraldehyde

Periodic acid does not cleave compounds in which the

hydroxyl groups are separated by an intervening –CH2 –
group, nor those in which a hydroxyl group is adjacent
to an ether or acetal function.
 Carbohydrates
Reactions of Monosaccharides

5. Reduction of Monosaccharides: Alditols

Aldoses (and ketoses) can be reduced with sodium borohydride to
compounds called alditols. For example, D-glucitol (or D-sorbitol)
CHO CH2OH

NaBH4
(CHOH)n (CHOH)n

CH2OH CH2OH

Aldose Alditol
 Carbohydrates
Disaccharides

• Disaccharides are
carbohydrates that yield
two monosaccharide
molecules on hydrolysis.
e.g. 1)sucrose,
2)lactose,
3)maltose

• Structurally,
disaccharides are
glycosides in which the
alkoxy group attached to
the anomeric carbon is
derived from a second
sugar molecule.
 Carbohydrates
Sucrose Disaccharides

• Ordinary table sugar (C12H22O11)

• Acid hydrolysis yields D-glucose and D-fructose.
• Sucrose is a nonreducing sugar; it gives negative tests with
Fehling’s solution because neither the glucose nor the fructose
portion of sucrose has a hemiacetal group (both carbonyl
groups are present as full acetals (i.e. as glycosides).
 Carbohydrates

Polysaccharides
• Polysaccharides, also known as
glycans, consist of monosaccharides
joined together by glycosidic linkages.
• Polysaccharides that are polymers of a
single monosaccharide are called
homopolysaccharides; those made up
of more than one type of
monosaccharide are called
heteropolysaccharides.
• Homopolysaccharides are also
classified on the basis of their
monosaccharide units.
• A homopolysaccharide consisting of
glucose monomeric unit is called a
glucan, one consisting of galactose
units is a galactan, and so on.
 Carbohydrates
Polysaccharides
• Three important
polysaccharides, all of which
are glucans, are starch,
glycogen, and cellulose.

• Starch is the principle food

reserve of plant.
• Glycogen functions as a
carbohydrate reserve for
animals.
• Cellulose serves as structural
material in plants.
 Carbohydrates
Carbohydrate Antibiotics

Carbohydrate antibiotics refers to microbial metabolites (mainly from

Actinomyces species) having antibacterial and antifungal properties and which
are carbohydrates or contain a carbohydrate component in their chemical
structure. Types include the aminoglycosides, macrolides, nucleoside analogs,
and glycosylated aromatic structures NH
NH
HN NH2
H2N NH
• One of the important discoveries in OH OH Streptidine
carbohydrate chemistry was the
OH
isolation of the carbohydrate
O
antibiotic called streptomycin. O
CHO L-Streptose
H3C
• Streptomycin is made up of three HO
O
HO
unusual components. O
2-Deoxy-2-methylamino-L-glucopyranose
R R'
R = NHCH3
R' = CH2OH
• The glycosidic linkage is nearly HO
always  . Streptomycin