 Tannins

◦ Tannins are secondary metabolites of

plants, heterogenous, non-
nitrogenous, HMW polyphenolic in
nature.
◦ Complex substance usually occurs as
mixtures of polyphenols that are
difficult to separate because they do
not crystallize.
◦ 1796: use tannin to denote
substances in plant extracts which were able to
combine with protein of animal hides, prevent
their putrefaction and convert them into
leather.
◦ Detection:
by tanning test
(Goldbeater’s skin test);
by adsorption on
standard hide powder.
“Tannis can be classified (general)
into TRUE and PSEUDOTannis”

MW ranging from 1000 to

5000.
 Solvent for extraction: water–acetone or
water–alcohol mixture.
 Separation: Chromatography
 Non – crystallizable
 Tannin + water = ???
 They cause precipitation of gelatin and
alkaloids thus making it as _________ and
__________
 Protein precipitant/protein inhibitor
 Present in greatest quantity in dead or drying
cells
 Contribute a protective function in barks and
heartwoods
 Upon polymerization it will produce an insoluble
red – colored product called as
phlobaphenes
 They form dark blue or greenish black soluble
compounds with FeCl3 and deep red with
potassium ferricyanide and ammonia.
 They are precipitated by salts of Cu, Pb, Sn and
strong aqueous potassium dichromate (or 1%
chromic acid) solution
 Commercial tannins
◦ Used in the leather industry
◦ Obtained from quebracho, wattle,
chestnut and myrobalsams

 Pharmaceutical tannins
◦ Prepared from oak galls and yield
glucose and gallic acid upon hydrolysis
 the galloyl units are
bound to diverse polyol-, catechin-, or
triterpenoid units
the galloyl units (at least
2) are C-C coupled to each other, and do
not contain a glycosidically linked catechin
units.

Based on Phytochemistry of Medicinal Plants

published on Journal of Pharmacognosy and
Phytochemistry, 2013
 glycosidic in nature,
bounded to gallotannin or ellagitannin
oligomeric or
polymeric proanthocyanidins formed by
linkage of C-4 of one cathecin with C-8 or
C-6 of the next monomeric catechin

Based on Phytochemistry of Medicinal

Plants published on Journal of
Pharmacognosy and Phytochemistry, 2013
 Hydrolyzable tannins – pyrogallol
tannins
◦ these esters are easily hydrolyzed by tannase or
HCl and H2SO4 to yield phenolic acid and sugar;
◦ blue black in color with FeCl3
◦ do not precipitate with Bromine T.S
◦ Glycosidic in nature
◦ On dry distillation produces gallic acid then
converted to pyrogallol
 Examples of hydrolyzable tannins:
– gallic acids
- hexahydroxy-diphenic
acid; ex: geraniin; tellimagrandins 1 and 2
 Examples:
◦ Myrobalon
◦ Bahera
◦ Witch hazel
 Nonhydrolyzable or Condensed tannins
◦ Heating with HCl yield phlobaphenes like
phloroglucinol/ dark green color with FeCl3
◦ They are not readily hydrolyzed to simpler
molecules and they do not contain a sugar
moiety.
◦ Aka __________

flavan-3,4-diols
 Nonhydrolyzable cont…
◦ Can form – give the
characteristic red color to many drugs such as
red cinchona;
◦ Dark green color produced with FeCl3 –
cathecol - tannins
◦ precipitate with Bromine T.S

◦ Examples:
 Black catechu, Pale catechu, Kinos
 General test for hydrolyzable/condensed
tannins
 Match stick is dipped in tannin extract
followed by HCl & warmed near a flame it
turns in color
 Rationale: Hydrolysis of tannins produce
phloroglucinol that will react to lignin and
producing pink color.
 Pseudotannins (false tannin)
◦ they do not form leather but yield color with
iron salts
◦ LMW compared to true tannins
◦ (-) result to goldbeater’s skin test

 They have catechins which give rise to the

peculiar odor.
 Examples of pseudotannins:
– from rhubarb and plant
containg gallitaninns
– from catechu, acacia, cutch,
tea
– coffee, nux vomica
- ipecacuanha
 Complex – tannins
◦ Newly discovered group of tannins,
biosynthesized from both hydrolyzable
and condensed tannins.
◦ 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.
 Goldbeater’s Skin Test - When gold
beater skin or ox skin is dipped in HCl &
treated with 1% FeSO4 solution, after washing
with water it gives a blue / black color.
 Gelatin Test
 Phenazone Test
 Test for catechin
 Test for chlorogenic acid
◦ (positive result: green color)
 (1)
 (2)
 (3)
 diuretics
 Anti-tumor (stomach and duodenal)
 Anti-inflammatory
 Anti-oxidant
 Hemostatic agent
 Black Catechu (Heartwood)
 SN: Acacia catechu /Acacia chundra
 FN: Leguminosae
 Constituents: catechin & quercetin
 Chemical Test:
1. it gives a pink color with vanillin & HCl
2. aqueous extract of drug when treated with lime water
gives a brown color
 Use/s: Astringents, treatment of ulcers,
diarrhea, & in tanning industry.
 Pale Catechu Leaves
 SN: Uncaria gambir
 FN: Rubiaceae
 Chemical Constituents:
◦ Chlorophyll, catechu red & gambier fluorescein.
◦ 7.33% catechins, 22-50% catechutannic acid
 Chemical Test:
◦ Alcoholic extract of drug when treated with NaOH
& light petroleum ether shows green fluorescence.
Uses: Astringents, treatment of ulcers,
diarrhea, & in tanning industry.
 Kinos (juice obtained
from trunk of
Pterocarpus marsupium)
 FN: Leguminosae
 Occurs as small shiny
reddish black pieces
 Chemical Constituents &
Uses:
◦ Same as catechu
 obtained from gall wasps Adleria
gallaetinctoria
 Family: Fagaceae
 Collection:
◦ Summer gall wasps lay eggs on the twigs;
◦ It penetrates the soft epidermis of the plant &
soon forms a larvae which eventually develops
into galls.
◦ Ideally galls should be collected before the
mature insect comes out.
 Chemical Constituents:
◦ Chinese galls contain 75%
tannic acid as compared to
60% in Turkish galls.

 Use: Astringent
 Extraction of tannic acid from
gall:
1. A mixture of alcohol-ether is added to
galls.
2. When water is added to this extract the
tannic acid enters the alcohol layer.
3. The ether layer can be discarded.
4. After precipitation with a non-polar
solvent it occurs as a white shiny
powder.
 Nutgall
◦ Quercus infectoria (twig) – (Fagaceae)
◦ Cynips tinctorius (insect)
◦ Larva- starch grains;
◦ Chrysalis stage - gallic acid( 3,4,5 trihdroxy
benzoic acid) a phenolic acid
◦ Wings develop- tannic acid formed;
◦ Insects emerge from the gall- tannic acid
becomes more porous and called white gall.
 Constituents:
◦ tannic acid (50-70%) – it is a mixture of esters
of gallic acid with glucose whose exact
composition varies according to its source –
treatment of bedsores, minor ulceration
◦ Gallic acid 2-4 %
◦ Ellagic acid
◦ Starch and resins
◦ Gallotannic acids – mixture of esters of gallic
acid with glucose
 SN: Terminalia chebula
 FN: Combretaceae
 Chemical Constituents:
◦ Gallic acid, ellagic acid, glucose, fructose,
sorbitol & active constituent chebulic acid.
 Uses:
◦ Astringent, wound healing antiseptics
 SN: Terminalia belerica
 FN: Combretaceae
 Chemical Constituents:
◦ Gallic acid, ellagic acid
 Uses
◦ Same as myrobalon
 (Witch Hazel/ Hazel
nut)
 Leaves of Hamamelis virginiana
 Family Name: Hamamelidaceae
 Constituents:
◦ Hamamelitannin – astringent and
hemostatic
◦ Gallic acid, resins, fats and bitter principle
 SN: Coffee arabica
 Family: Rubiaceae
 Caffeine which is salt of chlorogenic acid, caffeol,
enzymes & other phenolic principles.
 Use/s: Stimulant, diuretic
 Chemical Test:
◦ 1.Murexide test- caffeine when Δ with HCl & potassium
chlorate gives a residue which on exposure to ammonia
vapors gives purple color.
◦ 2.Caffeine forms a white precipitate with tannin solution
 Tea - prepared leaves of Camelia sinensis
[Thea sinensis]
 Family: Theaceae
 Chemical Constituents:
◦ Caffeine, theobromine, theophylline, oxidase
enzyme & tannins
 Uses & chemical Tests:
◦ Same as coffee
 - from dried false fruit of
Crataegus monogyna & C. laevigata
 Family: Rosaceae
 Constituent/s:
◦ Fruits – 1 – 3% oligomeric procyanidins
 Use/s:
◦ Mild cardiac tonic
 – Alchemilla xanthochloratannis
 Family: Rosaceae
 Constituent/s:
◦ NLT 6% tannins expressed as pyrogallol
◦ Ellagitannins
 Use/s:
◦ Astringent against bleeding
◦ Diarrhea
◦ Menorrhagia