PHARM.

D Chemical Pharmacognosy- I Lecture 32 May 19th, 2011

TANNINS - III

M. Ahsan Khalid, B.Pharm, Pharm. D B.Pharm, M.Phil Scholar (RIPS/RIU) HIPSHIPS-HUKIC

Condensed Tannins

Are polymers of 2 to 50 (or more) flavonoid units that are joined by carboncarboncarbon bonds, which are not susceptible to being cleaved by hydrolysis. All hydrolyzable tannins and most condensed tannins are water soluble some very large condensed tannins are insoluble. insoluble.

Condensed Tannins

Condensed tannins are oligomeric and polymeric proanthocyanidins consisting of coupled flavan-3-ol (catechin) units. (oligomeric or polymeric proanthocyanidins =condensed proanthocyanidins = condensed tannins). Biosynthetically the condensed tannins are formed by the successive condensation of the single building blocks (up to more than 50 may be included in a single condensed tannin). The coupling pattern of the catechin units in condensed tannins can vary considerably.

NOTE: Oligomeric: a polymer that consists of 2, 3, or 4 monomeres. Polymer: Any of numerous natural and synthetic compounds of usually high molecular weight consisting of up to millions of repeated linked units, each a relatively light and simple molecule.

Condensed Tannins/Proanthrocyanidins

They are not readily hydrolysed to simpler molecules and they do not contain a sugar moiety (unlike hydrolysable tannins). On treatment with acids or enzymes, enzymes, condensed tannins are converted into red insoluble compounds known as phlobaphenes. phlobaphenes.

Condensed Tannins/Proanthrocyanidins

Phlobaphenes give the characteristic red colour to many drugs such as red cinchona bark, which bark, contains these phlobatannins and their decomposition products. These tannins are therefore sometimes called catechol tannins (as they yield catechol). catechol). Like catechol itself, their (condensed tannin) solutions turn green with ferric chloride.

Plants rich in Condensed Tannins

Barks: Barks: cinnamon, wild cherry, cinchona, willow, acacia (wattle, mimosa), oak bark, Hamamelis. Hamamelis. Flowers: Flowers: Lime and Hawthorn Seeds: Seeds: cocoa, guarana, kola guarana, Fruits: Fruits: cranberries, grapes, hawthorn Leaves Hamamelis, hawthorn, tea leaves Hamamelis, (especially green tea) Extracts and dried juices: catechu, acacia, East Indian kino and eucalyptus kino

Complex Tannins

The structures of the complex tannins are built up from a gallotannin unit or an ellagitannin unit, and a catechin unit.

Fig: Acutissimin A, the usual representative of the complextannins.

Hamamelis leaf & bark

Some drugs (e.g. tea, Hamamelis leaves and Hamamelis bark) contain both hydrolysable and condensed tannins.

Hamamelis Leaf

Definition: Witch hazel leaves consists of the dried leaves of Hamamelis virginiana, Hamamelidaceae). It should contain no less than 30% tannins.

Hamamelis Flowers

Witch hazel leaves Hamamelis Constituents

Gallitannins Ellagitannins Free gallic acid Proanthrocyanidins Bitter principles Volatile oil

Hamamelis - Uses

Astringent Haemostatic (Both due to tannins)

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).

It should be carefully distinguished from black catechu or cutch. The plant is Native to Malaysia and Indonesia.

Catechu: Uses

Uses in medicine as an astringent.

Catechu: Constituents
Catechins Catechutannic acid Catechu red Quercetin Gambir-florescin Gambir

Catechu: Allied Drugs

Cutch or black catechu

BLACK CATECHU BIOLOGICAL SOURCE -. Heart wood of Acacia catechu /Aacacia chundra Family- leguminosae Preparation: Pieces of heartwood are boiled with water till the drug is exhausted & the resulting solution is stored in clay pits wherein the semi solid mass known as cutch gets absorbed & the liquid remaining behind is dried & cut into small pieces. Chemical Constituents: Contains acacia catechin & quercetin Chemical Test: 1. it gives a pink colour with vanillin & HCl 2. aqueous extract of drug when treated with lime water gives a brown colour. Uses: Astringents, treatment of ulcers, diarrhoea, & in tanning industry.

PALE CATECHU BIOLOGICAL SOURCE -. leaves of Uncaria gambier Family: rubiaceae Preparation: The leaves are boiled with water & resulting solution is concentrated to obtain pale yellow viscous solution which is further dried to obtain cylindrical pieces. Chemical Constituents: Pale catechu contains chlorophyll, catechu red & gambier fluorescein. Chemical Test: Alcoholic extract of drug when treated with NaOH & light pet ether shows green fluorescence. Uses: Same as black catechu General test for condensed tannins is the MATCH

STICK TEST: When a match stick is dipped in tannin extract followed by HCl & warmed near a flame it turns pink in colour. The wood of the matchstick has lignin. Upon hydrolysis of the tannins due to HCl, phloroglucinol is formed which reacts with the lignin of the wood to produce the pink colour.

Kinos

Kino: applies to a number of dried juices, rich in phlobatannins. phlobatannins. Were formally used for their astringent properties: diarrhoea (e.g. lozenges) Include eucalyptus kino or red gum from Eucalyptus rostrata.

Tannins - Properties

WaterWater-soluble Also soluble in dilute alkali, alcohol, glycerol and acetone Slightly soluble in other organic solvents. Solutions precipitate heavy metals, alkaloids, glycosides and gelatin.

Tannins Properties:

If a dilute ferric chloride solution is added to an aqueous extract of hamamelis leaves (containing both types of tannins), a blue colour is produced which then changes to orangeorangegreen as more ferric chloride is added.

Free gallic acid gives an orange colour with potassium iodate.

Tannin Properties: Hydrolysable or Condensed?

With ferric salts, gallo-tannins and ellagi-tannins give blue-black salts, galloellagiblueprecipitates. Condensed tannins give brown-green precipitates. brownCondensed tannins turn red with vanillin and HCL. HCL.

GalloGallo-tannins give a pink colour with potassium iodate. Ellagitannins react (are coloured) with nitrous acid in the presence of acetic acid. Colour reaction: pink purple blue. acid. blue.

TLC is used to analyze extracts (visualized under UV light and with the reagents mentioned above) HPLC can also be used.

PseudoPseudo-Tannins

PseudoPseudo-tannins are compounds of lower molecular weight than true tannins and they do not respond to the goldbeaters skin test. Gallic acid: rhubarb Catechins: catechu, acacia cutch, many Australian kinos, cocoa, guarana and many other drugs containing condensed tannins Chlorogenic acid: coffee (particularly unroasted) and nux Vormica (a small quantity only). Ipecacuanhic acid: ipecacuanha acid:

COFFEE
Biological Source -.: seeds of Coffee arabica Family: Rubiaceae Geographical Source -.: South India, Indonesia Collection: The unripe fruit is dark green & is collected when it turns red. Each fruit has 2 locules containing one seed each. Chemical Constituents: Contains caffeine which is a salt of chlorogenic acid, volatile oil known as caffeol, enzymes &other phenolic principles. caffeol, Use: Stimulant, diuretic & source of caffeine Chem. Test: 1.Murexide test- caffeine when heated with HCl & potassium testchlorate gives a residue which on exposure to ammonia vapours gives purple colour. colour. 2.Caffeine forms a white precipitate with tannin solution

TEA
BIOLOGICAL SOURCE -.: prepared leaves of Thea sinensis Family: Theaceae GEOGRAPHICAL SOURCE -. India, Srilanka Chemical Constituents: Caffeine, theobromine, theophylline, oxidase theobromine, theophylline, enzyme & tannins Uses: & chem. Tests: Same as coffee

Camellia sinensis/Thea sinensis

Polyphenols strong antianti-oxidant effect. Leaves: cancer preventative (Japan). Clinical trials indicate that green tea helps to promote weight loss and treat hepatitis. May prevent tooth decay. Trials show a hypotensive effect. NB: Green-tea: caffeine Greenneeded for effects.