INTRODUCTION TO

PHYTOCHEMISTRY
INTRODUCTION TO PHYTOCHEMISTRY
The science which studies the chemistry of
phytogenic products (natural
products/constituents) ,which have
therapeutic activity or/and have
Pharmaceutical industry uses.

Constituents: These are the chemicals in

plants that give them their pharmacological
or physiological activity.
 CONSTITUENTS
Two types:
1) Inert Constituents: These are chemical
compounds present in plants which do not
possess any definite therapeutic values but are
useful as adjuncts either in the formulation of a
drug or in surgery.
Examples:
a) Plant Drugs: The following inert constituents are
present in plants, namely:
Cellulose : used as combination binders and
disintegrants in tabletting.
 Starch : As pharmaceutical aid i.e.; tablet filler,
binder and disintegrant
Albumin : emulsifiers
Lignin : To precipitate proteins, and to stablise
emulsions
2) Active constituents: These are the chemical
entities that are solely responsible for the
pharmacological, microbial or in a broader-
sense therapeutic activities of the plant.
Constituents such as alkaloids, glycosides,
steroids, terpenoids and tannins are members
of this particular category.
TANNINS
 TANNINS
The term 'tannin' was first applied by Seguin in
1796 to denote substances present in plant
extracts which were able to combine with protein
of animal hides, prevent their putrefaction and
convert them into leather.

On this basis a tannin is a substance which is

detected qualitatively by a tanning test (the
goldbeater's skin test) and is determined
quantitatively by its adsorption on standard hide
powder.
 This definition excludes simpler phenolic
substances, often present with tannins, such as

gallic acid,
catechins and
chlorogenic acid,

although they may under certain conditions give

precipitates with gelatin and be partly retained by
hide powder.
 Such substances of relatively low molecular
weight are called 'pseudo-tannins'.

Most true tannins have molecular weights of

from about 1000 to 5000.

Many tannins are glycosides

 Types of true tannins
Two main groups of tannins are usually
recognized;

The hydrolysable tannins and

The condensed tannins (proanthocyanidins).

 Hydrolysable tannins
These may be hydrolysed by acids or enzymes such as
tannase.

They are formed from several molecules of phenolic

acids such as gallic and hexahydroxydiphenic acids which
are united by ester linkages to a central glucose
molecule.
COOH
OH OH
HO OH HO OH

HO OH
COOH COOH
OH
Hexahydroxydiphenic acid
Gallic acid
 Hydrolysable tannins
Their solutions turn blue with iron salts (e.g.
FeCl3)

They were formerly known as pyrogallol

tannins, because on dry distillation gallic acid
and similar components are converted into
pyrogallol.
 Types of Hydrolysable tannins
There are two principal types of hydrolysable
tannins

1) Gallotannins : composed of gallic acid units

2) Ellagitannins: which are composed of

hexahydroxydiphenic acid units.
 Hydrolysable tannins
Gallotannins Ellagitannins

Glucose
o
oH oH oH oH oH
o
o oH oH
o oo
o o
Glucose
oH oH
oH
Plants containing Hydrolysable tannins
Gallotannins: rhubarb, cloves, red rose petals,
bearberry leaves, Chinese galls, Turkish galls,
hamamelis, chestnut and maple.

Ellagitannins: pomegranate rind, pomegranate

bark, eucalyptus leaves, kousso, some
Australian kinos, chestnut (Castanea spp.) and
oak bark
 Condensed Tannins
Are polymers of 2 to 50 (or more) flavonoid
units that are joined by carbon-carbon bonds.

Flavone
 Condensed Tannins
Unlike hydrolysable tannins, these are not
readily hydrolysed to simpler molecules and
they do not contain a sugar moiety.

On treatment with acids or enzymes

condensed tannins are converted into red
insoluble compounds known as
phlobaphenes.
 Condensed Tannins
Phlobaphenes give the characteristic red colour to
many drugs such as red cinchona bark, which contain
these phlobatannins and their decomposition
products.

On dry distillation they yield catechol and these

tannins are therefore sometimes called catechol
tannins.

Their solutions turn green with ferric chloride (FeCl3)

Condensed tannins(proanthocyanidins) Some drugs

(e.g. tea, hamamelis leaves and hamamelis bark)
contain both hydrolysable and condensed tannins.
 Plant drugs rich in condensed tannins
Barks: cinnamon, wild cherry, cinchona, willow, acacia,
hamamelis

Roots and rhizomes: krameria (rhatany) and male fern

Flowers: lime and hawthorn

Seeds: cocoa, kola and areca

Fruits: cranberries, grapes (red wines)

Leaves: hamamelis, tea

Extracts and dried juices: catechu, acacia and, butea gum and
eucalyptus gum
 Pseudotannins
Pseudotannins are compounds of lower
molecular weight than true tannins and they do
not respond to the goldbeater's skin test.
Examples include;
Gallic acid: rhubarb
Catechins: catechu, acacia, cocoa and many drugs
containing condensed tannins
Chlorogenic acid: coffee (particularly unroasted)
and nux vomica (a small quantity only)
lpecacuanhic acid: ipecacuanha
 Properties and tests
Tannins are soluble in water, dilute alkalis,
alcohol, glycerol and acetone, but generally
only sparingly soluble in other organic
solvents.

Solutions precipitate heavy metals, alkaloids,

glycosides and gelatin.
 Properties and tests
With ferric salts, gaIlotannins and
ellagitannins give blue-black precipitates and
condensed tannins brownish-green ones.

If a very dilute ferric chloride solution is

gradually added to an aqueous extract of
hamamelis leaves (which contains both types
of tannin), a blue colour is produced which
changes to olive-green as more ferric chloride
is added.
 Other useful tests
I. Goldbeater's skin test.
Soak a small piece of goldbeater's skin in 2% hydrochloric
acid; rinse with distilled water and place in the solution to
be tested for 5 min. Wash with distilled water and transfer
to a 1 % solution of ferrous sulphate. A brown or black
colour on the skin denotes the presence of tannins.

Goldbeater's skin is a membrane prepared from the

intestine of the ox/calf and behaves similarly to an
untanned hide.

2. Gelatin test.
Solutions of tannins (about 0.5-1 %) precipitate a 1 %
solution of gelatin containing 10% sodium chloride.

Gallic acid and other pseudotannins also precipitate gelatin

if the solutions are sufficiently concentrated.
 Other useful tests
3. Phenazone test.
To about 5 ml of an aqueous extract of the drug add 0.5 g
of sodium acid phosphate; warm, cool and filter. To the
filtrate add 2% solution of phenazone. All tannins are
precipitated, the precipitate being bulky and often
coloured.

4. Test for catechin.

Catechins on heating with acids form phloroglucinol and
they can, therefore, be detected by a modification of the
well known test for lignin. Dip a matchstick in the plant
extract, dry, moisten with concentrated hydrochloric acid
and warm near a flame. The phloroglucinol produced
turns the wood pink or red.
 Other useful tests
5. Test for chlorogenic acid.
An extract containing chlorogenic acid when
treated with aqueous ammonia and exposed
to air gradually develops a green colour
 Tannin toxicity
If ingested in excessive quantities, tannins
inhibit the absorption of minerals such as iron
which may, if prolonged, lead to anemia
This is because tannins are metal ion
chelators, and tannin-chelated metal ions are
not bioavailable.
Tannins only reduce the bioavailability of plant
sources of iron, also known as non-heme.
 Tannin toxicity
Animal sources, or heme iron absorption will
not be affected by tannins. Tannic acid does
not affect absorption of other trace minerals
such as zinc, copper, and manganese in rats
Tannins have been shown to precipitate
proteins, which inhibits in some ruminant
animals the absorption of nutrients from high-
tannin grains such as sorghum.
 Tannin toxicity
Foods rich in vitamin C help neutralize tannin's
effects on iron absorption.

Adding lemon juice to tea will reduce the

negative effect of tannins in iron absorption as
well.

Adding milk to coffee and tea has very little to no

influence on the inhibitory effect of tannins.
Medicinal and biological properties
Tannins are sometimes used to treat poisons
from poison oak or from bee stings, causing
instant relief.

Tannins have shown potential antiviral,

antibacterial and antiparasitic effects.

Tannins have been used for immediate relief of

sore throats, diarrhoea, dysentery,
haemorrhaging, fatigue, skin ulcers and as a
cicatrizant on gangrenous wounds
 Anti-HIV activity has also been demonstrated.

Proanthocyanidins (condensed tannins) are

associated with the beneficial effects of
various herbs and infusions produced from
them.

The antitumour activity of green and black tea

has been extensively researched in recent
years with positive findings.
 Cranberry juice has long been used for
reducing bacterial infections of the bladder.

Used as antidotes in poisoning by heavy

metals, alkaloids and glycosides.
 Styptics/ Astringent to stop bleeding
(Haemorrhoids, Ulcers).
Tannins are used industrially to clarify wine
and beer.
TANNIN CONTAINING HERBS
 Hamamelis leaf (witch hazel leaves)
Definition: Witch hazel
leaves consists of the
dried leaves of
Hamamelis virginiana,
Hamamelidaceae).
Uses:
Used in the treatment of
wounds
As an astringent
 Catechu
Definition: Gambir or
pale catechu is a dried
aqueous extract
prepared from the
leaves and young twigs
of a climbing shrub,
Uncaria gambir
(Rubiaceae).
Uses:
As an astringent