Tannins

Tannins
• Tannins are complex organic, non-nitrogenous derivatives of
polyhydroxy benzoic acids which are widely distributed in the plant
kingdom.
• Many of them are glycosidal in nature. The gallotannins on hydrolysis
yield a sugar and gallic acid. Tannins are pale yellow to light brown-
red amorphous substances widely distributed in plants and used
chiefly in tanning leather, dyeing fabric, and making ink. They form
colloidal solutions with water and their aqueous solutions are acidic in
nature.
Properties of Tannins
• Tannins are non-crystallizable, amorphous compounds.
• They are soluble in water, ethyl alcohol, glycerol, acetone and dilute
alkalies.
• Their aqueous solution shows an acidic reaction and a sharp astringent
taste.
• Most of the tannin compounds cause precipitation of solutions of
alkaloids, glycosides, gelatin, heavy metals and protein.
Classification of Tannins

• Tannins are classified as-

• True tannins: These are complex phenolic compounds of high
molecular weights ranging from about 1000 to 5000. They display the
general properties of tannins. True tannins can be sub-classified into
• a) Hydrolysable tannins: As the name implies these tannins are
hydrolysable by mineral acids or enzymes such as tannase. Their
structures involve several molecules of polyphenolic acids such as
gallic, hexahydroxydiphenic or ellagic acid, bounded through ester
linkages to a central glucose molecule.
• On the basis of the phenolic acids produced after the hydrolysis, they
are further categorized under
• Gallotannins: composed of gallic acid.
• Ellagitannins: contain hexahydroxydiphenic acid which after intra-
esterification produces ellagic acid.
• Hydrolysable tannins are sometimes referred to as pyrogallol tannins
as the components of phenolic acids on dry distillation are converted
to pyrogallol derivatives. The hydrolysable tannins are soluble in
water and their solution produces blue color with ferric chloride.
HO COOH HO HO

HO COOH HO
HO
OH O
OH
HO O
gallic acid
HOOC OH OH
HO
O

OH OH

HO hexahydroxydiphenic acid ellagic acid

OH

pyrogallol
• b) Condensed tannins: They are also called as non-hydrolysable
tannins, phlobatannins or proanthocyanidins. They are related to
flavonoid pigments, because they are formed via derivatives of
flavones, like catechin (or flavan-3-ol) or flavan-3,4-diols. They are
much resistant to hydrolysis. On treatment with enzymes or mineral
acids, they are polymerized or decomposed into red colored substances
called phlobaphenes. The phlobaphens are insoluble in water and
indicate the typical brownish-red colour of many plants and drugs
colour. On dry distillation they yield catechol derivatives. Tannins with
ferric chloride produce brownish-green color. OH

HO O
OH

OH

Catechin
OH
c) Complex tannins: are tannins in which a catechin unit is bound
glycosidically to a gallotannin or an ellagitannin unit.
2. Pseudo tannin: Pseudotannins are simple phenolic compounds of
lower molecular weight. They do not respond to the goldbeater's skin
test and may under certain conditions, e.g. in concentrated solutions,
give precipitates with gelatine. E.g.: Gallic acid, chlorogenic acid or the
simple phenolics such as catechin are pseudotannins.
Identification of Tannins
i. Test with ferric chloride: To the solution of tannins add ferric
chloride solution. Hydrolysable tannins produce blue-black
precipitate while condensed tannins show brownish green
precipitate.
ii. Gelatin test: To a solution of tannin,
aqueous solution of 1% gelatin and 10%
sodium chloride are added. A white buff
colored precipitate is formed. Conforms the
presence of tannins and pseudo tannins.

iii. Bromine water: Add bromine water to an

aqueous extract of the drug. Condensed
tannins give a buff-colored precipitate, but
hydrolysable tannins do not form any
precipitate.
iv. Goldbeater's skin test:
A small piece of goldbeater skin (membrane prepared from the intestine
of an ox) is soaked in 20% hydrochloric acid, rinsed with distilled water
and placed in a solution of tannin for 5 minutes. The skin piece is
washed with distilled water and kept in a 1% solution of ferrous
sulphate. A brown or black colour is produced on the skin due to the
presence of tannins.
v. Phenazone Test: To 5 ml of aqueous solution of tannin containing
drug, add 0.5 g of sodium acid phosphate. Warm the solution, cool and
filter. Add 2 % phenazone solution to the filtrate. All tannins are
precipitated as bulky, colored precipitate.

vi. Match stick test (Catechin test): Matchstick contains lignin. A

match stick is dipped in aqueous plant extract, dried near burner and
moistened with concentrated hydrochloric acid. On warming near flame,
the matchstick wood turns pink or red due to formation of
phloroglucinol.
Quantitative determination of tannin:
a. Hide powder method: This is the most widely used on commercial
scale. A known amount of a reference sample of hide powder is added to
the drug extract. The difference in the dry weight of the extract before
and after treatment with hide powder is a measure for the tannin content.

b. Copper acetate method: Gravimetric method using copper acetate

as precipitant.
c. Agglutination method:
The erythrocytes are agglutinated (stick together) due to formation of a
sticky membrane on their surface in contact with tannins. The quantity
of red blood cells precipitated is proportional to the amount of
"astringent" tannin present.

d. Iodometric determination:
Tannins and pseudotannins quantitatively consume iodine from alkaline
medium due to their phenolic nature.
Isolation of Tannin
• Both hydrolysable and condensed tannins are highly soluble in water and
alcohol but insoluble in organic solvents such as solvent ether, chloroform,
and benzene.
• Tannin compounds can be easily extracted by water or alcohol. The general
method for the extraction of tannic acid from various galls is either with
water-saturated ether, or with mixture of water, alcohol, and ether.
• In such cases, free acids such as Gallic and ellagic acid go along with ether
while true tannin gets exracted in water. If the drug consists of chlorophyll
or pigment, it may be removed by ether.
• After extraction, the aqueous and ethereal layers are separately
concentrated, dried, and subjected to further isolation and purification using
various separation techniques of chromatography
Medicinal and biological properties
• Tannin-containing drugs precipitate proteins and have been
traditionally used as styptics (stop hemorrhage) and internally for the
protection of inflamed surfaces of mouth and throat.
• They play an important role in the treatment of burns. They form a
mild antiseptic protective layer on the surface of the injured skin
below which regeneration of new tissue takes place.
• Tannins have been employed as antidote in poisoning by heavy metals,
alkaloids and certain glycosides due to their precipitation as tannates.
• Recently tannins as most polyphenols
were proved to have a potent
antioxidant effect.
• Studies on the antitumor effect of
tannins proved that a strong activity is
obtained with ellagitannins. E.g.:
Tellimagrandin I.
• Certain tannins were proved to have
anti-herpesvirus properties. E.g.:
Tellimagrandin II.
Uses of Tannins
• Tannins are used in leather industry to transform raw animal skin to
leather due to their ability to cross-link with proteins (Tanning).
• Tannins produce different colors with ferric chloride according to the
type of tannin. Iron gall ink is produced by treating a solution of
tannins with iron(II) sulfate.
• Tannins are used in food industries to improve acceptance of many
beverages and foods when a degree of astringency is required.
• Tannin is a component in a type of industrial particle board adhesive.
• Tannins can be used for production of anti corrosive primer for
treatment of rusted steel surfaces prior to painting.
Black Catechu
• Biological Source: Black Catechu is a dried aqueous extract
prepared from the heartwood of Acacia catechu Wild.
• Family: Leguminosae.
• Chemical Constituents: Black Catechu contains a mixture of catechin
isomers, acacatechin (25-35%), gum (20-30%), quercitrin, quercetin,
catechu red and water. Acacatechin contains (-)-epicatechin.
Acacatechin is insoluble in cold water but soluble in hot water. It
undergoes oxidation to catechu tannic acid in the presence of water.
• Uses:
• Black Catechu is mainly used as an
ingredient of betal leaf (Paan) and
Paan masala.
• Black Catechu possesses cooling and
digestive properties.
• It is used in relaxed condition of
throat, mouth, gums, in cough and
diarrhoea.
• Externally as an astringent
medicament it is applied to ulcers,
boils, skin eruptions and in a number
of medicinal preparations.
Nutgalls
• Biological Source: Nutgall is a kind of gall on a tree with a nut-like
shape. The galls arise on young branches of the Quercus infectoria tree
when gall wasps sting the oak tree and deposit their larvae; the
chemical reaction causes an abnormality in the oak tree causing hard
balls to be formed.
• Chemical Constituents: Nutgalls contains gallotannic acid which is
official tannic acid. Tannic acid of is a hydrolyzable tannin which
yields gallic acid and glucose on hydrolysis. It also consists of gallic
acid, ellagic acid, sitosterol, methyl belulate and methyl oleanolate.
• Uses: Gallic acid

• Nutgall is the major source of tannic acid, Gallic acid

which is largely used in tanning and dyeing O Gallic acid

industry and for the manufacture of ink.
Gallic acid
• It is used medicinally as a local astringent O O
in ointments and suppositories.

Gallic O O Gallic acid

acid

Gallic Gallic acid Gallic acid

acid

Gallic acid Tannic acid

Sulla
Biological Source: Hedysarum coronarium
Family: Fabaceae
Chemical Constituents:
Richer in condensed tannins and flavonoids,
principally rhoifolin, quercetin, naringenin and
derivatives.
Uses:
• Induce collagen production
• Edible flower
• Cosmeceutical products preparation
Gambier or Pale catechu
• Biological Source: It is a dried aqueous
extract produced from the leaves and young
twigs of Uncaria gambier, family Rubiaceae.
• Chemical Constituents: Pale catechu
contains catechin and a phlobatannin,
catechutannic acid. It also contains quercetin,
catechu red, pyrogallol, fixed oil and waxes.
• Uses:
• Pale catechu is medicinally used as local
astringent.
• It is used in the treatment of diarrhea.
Hamamelis
Biological Source: Hamamelis virginiana
Family: Hamamelidaceae
Chemical Constituents:
Gallitannins, Ellagitannins, Free gallic acid,
Pro-anthocyanadins, Hamamelase
Uses
• Astringent
• Anti-hemorrhagic
• Anti-inflammatory
• Anti-carcinogenic
Grape Seed
Biological Source: Vitis vinifera
Family: Vitaceae
Chemical Constituents:
V. vinifera grape seeds were catechin (11%)
followed by epicatechin, epicatechin-3-O-
gallate, epicatechin 3-O-gallate-(4β→8)-
catechin (B1-3-O-gallate),
epicatechin(4β→8)epicatechin.
Uses:
Grape seed extract also reduces swelling caused
by injury and helps with eye disease related to
diabetes. Many people are interested in grape
seed extract because it contains antioxidants.