PHENOLIC

COMPOUNDS (II)

C. Tannin
D. Coumarin
E. Quinone
If you want to try a trick that can help you recognize a tannin when you taste it,
brew a cup of extra strong black tea. Tannins naturally occur in black tea and
their characteristics emerge when the tea is brewed a few minutes longer than
recommended. After brewing the tea, take a sip and you’ll immediately notice a
slight bitterness in the middle of your tongue and a dryness in the front of your
mouth — this is a tannin.
C. TANNINS
1. Tannins are water soluble oligomers, rich in phenolic
groups (polyhydroxy phenolic compounds).They are high
molecular weight phenolic compounds.

2. Tannin are widely distributed in plants, exist primarily in

woody plants. The word tannin means the ability of plant
extracts to tan leather. The term tannin is defined as
chemical structure or group of chemical compounds that
have tanning properties

3. Physical Properties
Color: Dark brown or reddish brown
State: Non-crystalline
Solubility: Soluble in water, alcohol, dilute alkalis,
glycerols and acetone.
 4. Tannins present in tea, fruit juices and wine are reported
to exhibit biological activities such as radical scavenging
(antioxidant) and protection against cardiovascular
disorder (known as ‘French paradox’).

5. Three major types of tannin :

a) Hydrolysable tannins
b) Condensed tannins
c) Pseudotannins
C. Tannins
C1. Hydrolysable tannins:
a) A hydrolysable tannin or pyrogallol-type tannin is a type
of tannin that can be hydrolyzed by enzymes or acids.
HCl/H2SO4 ) to yield gallic or ellagic acids.
b) They are formed by the combination of several
molecules of gallic acid and ellagic acid through ester-
linkages to central glucose molecule.
c) Ester of gallic acid are called gallo-tannins and ester of
ellagic acid are called ellagitannins.
C2. Condensed Tannins (proanthocyanidins)
Condensed tannins are formed through the polymerization of flavan-3-ol
(catechin) and flavan–3,4-diols (leucoanthocyanidins) 2-50 units
(typically 2-8 units) through linkages of various sites
Condensed tannins, also known as
proanthocyanidins, can contain
dozens of units of flavan-3-ols
(catechin) or flavan-3,4-diols
(leucoanthocyanidins).

These units have a complex

structure and are resistant to
hydrolysis; however, they can be
soluble in aqueous organic solvents
because of their structure

9
monomer
Pseudo tannins
Pseudo tannins are low molecular weight compounds associated
with other compounds. They do not change color during
the Goldbeater's skin test, unlike hydrolysable and condensed
tannins, and cannot be used as tanning compounds. Some
examples of pseudo tannins and their sources are:
D. COUMARINS
1. Coumarin is 5,6-benzo-2-pyrone and along with its various
derivatives occurs abundantly in plant families such as
Umbelliferae, Rutaceae, Leguminaceae, Orchidaceae,
Asteraceae, Guttiferae, Melastomaceae, Thymelaceae and
Solanaceae.

2. The name coumarin is derived from the Caribbean word ‘coumaro’

for the tonka tree from which coumarin with the characteristic
aroma of new-mown hay was isolated.

3. Coumarins play role in plant protection. In low concentration they

show synergistic activity with plant growth promoting. Biological
activity of coumarin is diverse and depend on their chemical
structure.
4. Most of these naturally occurring lactones are oxygenated at
C-7 position and hence 7-hydroxy coumarin, umbelliferone is
regarded as the parent compounds.

7-hydroxy coumarin

umbelliferone

5. Solubility of coumarins depend upon phenolic hydroxyl group

and the glycosidic bond.
6. Coumarins occur in plants in free form or as glycosides.
Aglycone coumarins are soluble petrol, benzene, ether,
chloroform diethyl ether,alcohol(non polar solvent)

7. Glycosides are soluble in water and alcohols(polar solvent)

8. Classification of coumarins: Coumarins are classified based

on the substitution in benzene rings and pyrone rings.

D1 : Simple coumarins with 5,6-benzene-2-pyrone skeleton with

hydroxyl, alkoxy, alkyl substituents both in benzene and the
pyrone ring.
7,8-Dihydroxycoumarin
3,7-Dihydroxycoumarin
D2 Furocoumarins : The chemical structure consists of a furan
ring fused with coumarins. Formed in result of furan ring
and coumarin condensation in 6,7 or 7,8 positions.

D3 Pyranocoumarins : Coumarins with added pyran ring(s).

Formed as a result of condensation of coumarin with 2’2’-dimethylpyrane
in positions 5,6; 6,7 or 7,8 and may have substitutes in any of rings.
D4 Benzocoumarins containing benzyl ring condensed
with coumarin in 3,4 positions.
7-(dimethylamino)-3,4-benzocoumarin

6-Amino-3,4-benzocoumarin

9. Example of naturally occurring coumarins

O O O O O
O
Linear furanocoumarin

psoralen
Angular furanocoumarin xylotenin
O O O
O O O

angelicin seselin
E. QUINONES
A class of cyclic organic compounds containing two
carbonyl groups, > C = O, either adjacent or separated
by a vinylene group, −CH = CH−, in a six-membered
unsaturated ring. The term quinone also denotes the
specific compound para- (p-)benzoquinone (C6H4O2).
E1 Naphthoquinones : possess the naphthalene skeleton and
can be represented as keto form of 1,4-dihydroxynaphthalene.
Examples of naphtoquinone
O OH O

OH

O O
lawsone juglone

Most of them are natural coloring dyes such as lawsone of

henna leaves (Lawsonia innermis) used to colour hair, juglone
(natural brown), lapachol (natural yelllow), deoxysantalin
(natural red), alkanin (natural red) and shikonin (natural
violet).
E2 Anthraquinones: possess the anthracene skeleton and
represented as 9,10-oxo-anthracenes. They occur both in
free state and as glycosides.

Natural anthraquinones are used both as natural dyes and

drugs. Many anthraquinones derivatives have also been used
as purgatives/laxatives. These anthraquinone derivatives
contain hydroxy, hydroxymethyl, methyl and carboxyl groups.
E3: Anthrones and anthranol : reduced form of anthraquinones
occur both in free state and as glycosides.
Anthrone

E4 Dianthrones are derived from 2 anthrone molecules, which

may be either identical or different.
Sennosides occurring in the leaves and fruits of Senna
acutifolia and Cassia angustifolia belong to the class of
dianthrones.
 conclusion
• Vast majority of plant based aromatic natural products are
phenols.
• Phenols constitute a large class of compounds in which a
hydroxyl group(-OH) is bound to an aromatic rings. These
phenolic compounds include simple phenols, flavonoids,
tannins, coumarin and quinones .
• Flavonoids;most abundant and important groups are found to
have many biological activities especially antioxidant activity,
(beside other activities; antimicrobial, antiulcer, anti arthritic,
estrogenic, anticancer and protein kinase inhibition). They also
serve as pollinating agent due to their bright colors that help to
attract insects
• The antioxidant activity of flavonoids is mainly contributed by the
presence of the phenolics rings in their structures. The phenolic
ring has the ability to scavenge the radicals that cause oxidation
by donating its hydrogen atoms to the radicals so as to make
them inactive.