TANNINS

Chapter Outline
 Introduction, Classification, Biosynthesis, Identification
 Detailed study of tannins in; Kino, Myrobalan, Catechu, Nutgall, Castanea, Krameria

Introduction

 Tannins comprise a large group of complex substances that are widely distributed in the plant kingdom
• Almost every plant family embodies species that contain tannins
 Chemically, tannins are complex substances; they usually occur as mixtures of polyphenols that are
difficult to separate because they do not crystallize
 Tannins are non-crystallizable compounds; with water, form colloidal solutions possessing an acid
reaction and a sharp ‘puckering’ taste
 Solutions of tannins precipitate heavy metals, alkaloids, glycosides and gelatin
 They form dark blue or greenish black soluble compounds with iron salts
 Tannins precipitate proteins from solution, and can combine with proteins rendering them resistant to
proteolytic enzymes
• When applied to living tissues this action is known as an ‘astringent’ action and forms the basis for
therapeutic application of tannins
 Considerable epidemiologic and experimental evidence suggests that prolonged utilization of certain
tannin-rich plant materials may be hazardous owing to their carcinogenetic potential
 The habitual chewing of betel nut (Areca catechu), an alkaloid-containing drug that is also rich in
condensed catechin tannin, has been linked to high rates of oral and esophageal cancer in India and South
Africa
 Even the drinking of ordinary tea (leaves of Camellia sincnsis) has been implicated
• Apparently, the British, who add milk to their tea, thereby binding the tannin, have a much lower
incidence of esophageal ‘obstruction’ than do the Dutch, who formerly drank large quantities of tea
without milk
 Experimentally, the subcutaneous injection into rats of aqueous extracts of tannin rich Areca catechu and
Rhus copallina produced a significant number of malignant mesenchymal tumors
 Tannins are of wide occurrence in plants and are usually found in greatest quantity in dead or dying cells
• They exert an inhibitory effect on many enzymes due to protein precipitation and hence, they may
contribute a protective function in barks and heartwoods

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 Uses of Tannins

 Tannin solutions are extremely valuable antidotes for alkaloidal poisoning

 An antidote in heavy metal poisoning
 An antidote in glycoside poisoning
 As astringent, help in wound healing and used in the treatment of burns
• In the treatment of burns, the proteins of the exposed tissues are precipitated and form a mildly
antiseptic, protective coat under which the regeneration of new tissues may take place
 Have been used traditionally as styptics (able to stop bleeding) and internally for the protection of inflamed
surfaces of mouth and throat
 The antitumor 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
 Anti-HIV activity has also been demonstrated
Absorbed tannic acid can cause severe central necrosis of the liver
 Solutions of tannins are utilized in the laboratory as reagents for the detection of gelatin, proteins, and
alkaloids (because of their precipitating qualities)
 Tannins are utilized in the process of vegetable tanning, which converts animal hides to leather (due to
their ability of protein precipitation)
• The tannin not only affects the pliancy and toughness of the leather, but also acts as a preservative
because of its antiseptic qualities
 Used on a commercial scale in the manufacture of inks (because they form deeply colored compounds
with iron salts)

Classification of Tannins

1. True Tannins
A. Hydrolysable tannins / Pyrogallol tannins
i. Gallitannins
ii. Ellagitannins
B. Condensed tannins / Non-hydrolysable tannins / Catechol tannins / Phlobaphenes
C. Complex tannins
2. Pseudotannins
Examples of pseudotannins: Gallic acid, catechins, chlorogenic acid, ipecacuanhic acid
True Tannins Pseudotannins
Molecular weight: 1000 to 5000 Molecular weight: Less than 500
Goldbeater’s skin test: Positive Goldbeater’s skin test: Negative

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 Hydrolysable tannins / Pyrogallol tannins
 These may be hydrolysed by acids or enzymes such as tannase
 They are formed from several molecules of phenolic acids (such as gallic acid and hexahydroxydiphenic
acid), which are united by ester linkages to a central glucose molecule
 They were formerly known as pyrogallol tannins
• Because on dry distillation gallic acid and similar compounds are converted into pyrogallol
 Hydrolysable tannins give blue color with ferric chloride solution
Gallitannins
 Composed of gallic acid units
 Examples: Rhubarb, cloves, red rose petals, bearberry leaves, Chinese galls, Turkish galls, hamamelis,
chestnut and maple
Ellagitannins
 Composed of hexahydroxydiphenic acid units
 Ellagic acid can arise by lactonization of hexahydroxydiphenic acid during the chemical analysis
 Ellagic acid is the depside of gallic acid
 Examples: Pomegranate rind, pomegranate bark, myrobalans, eucalyptus leaves, kousso, some Australian
kinos, chestnut (Castanea spp.) and oak bark
Depside is a class of compounds formed by condensation of a phenolic carboxylic acid (such as gallic acid) with a similar compound,
the reaction being between the carboxylic acid group on one molecule and a phenolic OH group on the other. Depsides are similar
to esters, except that the OH group is linked directly to an aromatic ring. In such compounds, the –O–CO– group is called a depside
linkage. Depsides are found in tannins and other natural products.
Lactonization is conversion into a lactone. Lactone is an organic compound containing an ester group –O–CO– as part of a ring

OH OH OH
HO HO HO
COOH

HO COOH HO COOH O CO

HO OH HOOC OH HOOC OH OC O
HO OH
OH
OH
Pyrogallol OH OH OH
Gallic acid
OH OH OH
2 molecules of gallic acid Hexahydroxydiphenic acid Ellagic acid

Condensed tannins (proanthocyanidins) / Non-hydrolysable tannins / Catechol tannins / Phlobaphenes

 Unlike hydrolysable tannins, these are not readily hydrolysed to simpler molecules and they do not contain
a sugar moiety
 These tannins are formed from the condensation of two or more flavan-3-ol (such as catechin) or flavan-
3,4-diol (such as leucoanthocyanidins)

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 On treatment with acids or enzymes, condensed tannins are converted into red insoluble compounds
known as phlobaphenes Flavan-3-ol
(Catechin) OH
 On dry distillation, condensed tannins yield catechol and these tannins
are therefore, sometimes called catechol tannins HO O
OH
 Give green color with ferric chloride solution
OH
 Examples: Barks (cinnamon, wild cherry, cinchona, willow, acacia,
OH
oak and hamamelis); Roots and rhizomes (krameria and male fern); Flavan-3,4-diol
Flowers (lime and hawthorn); Seeds (cocoa, guarana, kola and areca); OH

Fruits (cranberries, grapes (red wines), hawthorn);

Leaves HO O
OH
(hamamelis, hawthorn and tea, especially green tea); Extracts and
dried juices (catechu, acacia and mangrove cutches, East Indian kino, OH

butea gum and eucalyptus kino) OH OH

 Drugs containing both hydrolysable and condensed tannins: Tea, hamamelis leaves and bark
Complex tannins
 Tannins biosynthesized from both a hydrolysable tannin and a condensed tannin
 The union occurs through a C–C bond between the C–1 of the glucose unit of the ellagitannin and the C–
8 or C–6 of the flavan-3-ol derivative
 Examples: Quercus, Castanea, Rheum and Camellia

Biosynthesis of Tannins

 Tannins are biosynthesized via shikimic acid pathway

Phosphoenolpyruvic acid + Erythrose-4-phosphate

2-Keto-3-deoxy-7-phospho-D-glucoheptonic acid

3-Dehydroquinic acid

Gallic acid Hydrolysable Tannins

3-Dehydroshikimic acid

Shikimic acid

Chorismic acid

Prephenic acid
Phenylpyruvic acid p-Hydroxyphenylpyruvic acid

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 Phenyllactic acid p-Hydroxyphenyllactic acid
p-Coumaric acid
trans-Cinnamic acid (p-Hydroxycinnamic acid) C6-C3 units of flavonoids

Condensed Tannins
Tests for identification of Tannins

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 minutes
 Wash with distilled water and transfer to a l% solution of ferrous sulfate
 A brown or black color on the skin denotes the presence of tannins
 Goldbeater's skin is a membrane prepared from the intestine of the ox and behaves similarly to an untanned
hide
Gelatin test
 Solutions of tannins (about 0.5-l%) precipitate a l% solution of gelatin containing l0% sodium chloride
 Gallic acid and other pseudotannins also precipitate gelatin if the solutions are sufficiently concentrated
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 precipitates being bulky and often colored)
Test for catechin
 Catechins on heating with acids form phloroglucinol
 Therefore, they can 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
Test for chlorogenic acid
 An extract containing chlorogenic acid when treated with aqueous ammonia and exposed to air gradually
develops a green color

Crude Drugs (Nutgall, Hamamelis, Myrobalan, Catechu, Kinos, Castanea, Krameria)

Nutgall
 Nutgalls are the vegetable growths formed on the young twigs of the dyer's oak, Quercus infectoria (Fam.
Fagaceae), as a result of the deposition of the eggs of the gall wasp Adleria gallaetinctoriae

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 The dyer's oak is a small tree or shrub about 2 m high
Formation of galls
 Insects lay eggs on twigs
 Larvae come out from eggs and enter soft epidermis
 Larvae secretes enzyme that stimulates abnormal growth around larvae
 Starch in the tissue gets converted to sugars and stimulate cell division
 As starch disappears from the neighborhood of the insect, shrinkage occurs and a central cavity is formed
in which the insect passes through the larval and pupal stages
 Finally, if the galls are not previously collected and dried, the mature insect bores its way out of the gall
and escapes
 During these changes, the color of the gall passes from a bluish grey through olive green to almost white
 Galls are collected by the farmers of Turkey and Syria
 After drying, galls are graded according to color into three grades i.e. blue, green and white
Constituents
 Tannic acid [principal constituent]
 Gallic acid
 Ellagic acid
 Starch
 Resin
Uses
 As astringent and styptic, in medicines
 In tanning and dyeing industries
 In the manufacture of ink
Hamamelis leaf
 Hamamelis leaf is the dried leaf of Hamamelis virginiana (Fam. Hamamelidaceae)
 The plant is a shrub or small tree the attains a height of 8 meters and is found particularly in low, damp
woods
 The leaves are collected throughout the summer
• Dried in the open air, preferably under shade to preserve the green color
Constituents
 Gallitannins
 Ellagitannins
 Free gallic acid
 Proanthocyanidins
 Bitter principles
 Traces of volatile oil
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Uses
 Astringent, Anti-hemorrhagic (hemostatic)
Myrobalans ‫ ہڑہڑ‬/ ‫حلیلہ‬
 Myrobalans are the dried fruits of Terminalia chebula (Fam. Combretaceae)
 It is a tree common in India
 The immature fruits are black, ovoid and about 1-3 cm long
Constituents
 Tannins (20-40%)
 β-sitosterol
 Anthraquinones
 Fixed oil
Uses
 Astringent, Cathartic, Anti-caries agent
Catechu ‫کتھا‬
 Gambir or pale catechu is a dried, aqueous extract prepared from the leaves and young twigs of a climbing
shrub, Uncaria gambir (Fam. Rubiaceae)
Preparation
 Extract the leaves and young twigs with boiling water
 Evaporate the extract to a pasty consistency
 Divide it into cubes, which are then sun-dried
Constituents
 Catechins
 Catechutannic acid
 Catechu red
 Quercitin
 Gambir-fluorescin
Uses
 Used in medicines as astringent
Kinos
 The name 'kino' has been applied to a number of dried juices rich in phlobatannins and formerly used for
their astringent properties
 They include;
• Malabar kino from Pterocarpus marsupium (Fam. Leguminosae)
• Butea gum or Bengal kino from Butea frondosa (Fam. Leguminosae)
• Eucalyptus kino or red gum from Eucalyptus rostrata (Fam. Myrtaceae)
Castanea / Chestnut ‫سنگھاڑا‬
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 These are the nuts (fruits) of Castanea sativa (Fam. Fagaceae)
 Nuts are eaten raw, roasted or boiled like potatoes
 Leaves of Castanea sativa also have medicinal importance
Constituents
 Nuts contain; Protein, calcium, phosphorus, thiamine, riboflavin, niacin, tocopherols
 Leaves contain; Tannins, flavone glycosides, triterpenoids, ursolic acid, lupeol, botulin
Uses
 Nuts-extract is used as platelet inhibitor in thrombosis and atherosclerosis
 Nuts, crushed with vinegar and barley flour, are used against indurations of breast
 Leaves are astringent, antitussive and febrifuge (used for fevers and diseases of the respiratory tract)
 An infusion of leaves is used as a gargle in pharyngitis, proxysmal coughs, catarrh and whooping cough
Krameria
 It is the dried root of Krameria triandra (Fam. Krameriaceae)
Constituents
 Rhataniatannic acid
Uses
 Astringent, styptic, antidiarrheal, vulnerary
 Used for menorrhagia
 Topically for wounds, hemorrhoids and chilblains
 As a lozenge, gargle or mouthwash for gingivitis and pharyngitis
 For topical treatment of mild inflammations of oral and pharyngeal mucosa
Read Book (not notes) if you want to be a Good Professional

Hafiz Abdul Khaliq ♦ hakhaliq@yahoo.com ♦ pharmacist.hak@gmail.com

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