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 Module-4 Traditional system of medicine and
Introduction to Secondary Metabolites

Scope- This module includes role of Pharmacognosy in Allopathy and

various traditional system of medicine. Also include detailed
information on a number of secondary metabolites.

Learning outcomes-
1. Student will able to learn role of Pharmacognosy in Allopathy and
various traditional system of medicine like Ayurveda, Unani,
siddha, Homepopathy and Chineese system.
2. Student will able to learn the introduction, classification,
properties and chemical tests for a number of secondary
metabolites like Alkloids, Glycosides, Flavonoids, Resins, Tannins
and Volatile oils.
Alkaloids
 Alkaloids

Definition: the term “alkaloid” (alkali-like) is

commonly used to designate basic
heterocyclic nitrogenous compounds of plant
origin that are physiologically active.
Distribution and occurrence:
Rare in lower plants.
Dicots are more rich in alkaloids than
Monocots.
Families rich in Alkaloids: Apocynaceae,
Rubiaceae, Solanaceae and
Papaveracea.
Families free from Alkaloids: Rosaceae,
Labiatae
Distribution in Plant:
All Parts e.g. Datura.
Barks e.g. Cinchona
Seeds e.g. Nux vomica
Roots e.g. Aconite
Fruits e.g. Black pepper
Leaves e.g. Tobacco
Latex e.g. Opium
Forms of Alkaloids:
Free bases
Salts with Organic acids e.g. Oxalic,
acetic acids
Salts with inorganic acids e.g. HCl, H2SO4.
Salts with special acids:
e.g. Meconic acid in Opium
Quinic acid in Cinchona

Glycosidal form e.g. Solanine in Solanum.

Function in Plants
They may act as protective against insects
and herbivores due to their bitterness and
toxicity.
Source of nitrogen in case of nitrogen
deficiency.
They, sometimes, act as growth regulators in
certain metabolic systems.
They may be utilized as a source of energy in
case of deficiency in carbon dioxide
assimilation.
 Nomenclature:
Trivial names should end by "ine". These names
may refer to:
The genus of the plant, such as Atropine from
Atropa belladona.
The plant species, such as Cocaine from
Erythroxylon coca.
The common name of the drug, such as
Ergotamine from ergot.
The name of the discoverer, such as Pelletierine
that was discovered by Pelletier.
The physiological action, such as Emetine that
acts as emetic, Morphine means God of dreams
acts as narcotic.
A prominent physical character, such as Hygrine
that is hygroscopic.
 Prefixes and suffixes:
Prefixes:
"Nor-" designates N-demethylation or N-demethoxylation,
e.g. norpseudoephedrine and nornicotine.
"Apo-" designates dehydration e.g. apomorphine.
"Iso-, pseudo-, neo-, and epi-" indicate different types of
isomers.
Suffixes:
"-dine" designates isomerism as quinidine and
cinchonidine.
"-ine" indicates, in case of ergot alkaloids, a lower
pharmacological activity e.g. ergotaminine is less potent
than ergotamine.
 Physical Properties:
I- Condition:
Most alkaloids are crystalline solids.
Few alkaloids are amorphous solids e.g. emetine.

Some are liquids that are either:

Volatile e.g. nicotine and coniine, or
Non-volatile e.g. pilocarpine and
hyoscine.
II- Color:
The majority of alkaloids are colorless but some are
colored e.g.:
Colchicine and berberine are yellow.
Canadine is orange.
 Physical Properties:
III- Solubility:
Both alkaloidal bases and their salts are soluble in alcohol.
Generally, the bases are soluble in organic solvents and
insoluble in water
Exceptions:
Bases soluble in water: caffeine, ephedrine, codeine,
colchicine, pilocarpine and quaternary ammonium bases.
Bases insoluble or sparingly soluble in certain organic
solvents: morphine in ether, theobromine and theophylline in
benzene.

Salts are usually soluble in water and, insoluble or

sparingly soluble in organic solvents.
Exceptions:
Salts insoluble in water: quinine monosulphate.
Salts soluble in organic solvents: lobeline and apoatropine
hydrochlorides are soluble in chloroform.
Extraction, Purification and Isolation of
Alkaloids from Powdered plants
Extraction and purification
Method I:
The powder is treated with alkalis to liberates the free bases
that can then be extracted with water immiscible organic
solvents.

Method II:
The powdered material is extracted with water or aqueous
alcohol containing dilute acid. Alkaloids are extracted as
their salts together with accompanying soluble impurities.

Method III:
The powder is extracted with water soluble organic solvents
such as MeOH or EtOH which are good solvents for both
salts and free bases.
 Classification of Alkaloids
Biogenetic.
Based on the biogenetic pathway that form the alkaloids.

Botanical Source.
According to the plant source of alkaloids.

Type of Amines.
Primary, Secondary, Tertiary alkaloids.

Basic Chemical Skeleton

Phenylalkylamines:
e.g. Ephedrine CH2 CH CH3

NH2

Pyridine and piperidine

e.g. lobeline, nicotine
N N
H
Tropane
e.g. Atropine.
NCH3 OH
Quinoline
e.g.quinine and quinidine

N
Isoquinoline
e.g.Papaverine,Emetine
N

Phenantheren
e.g. Morphine
Indole
e.g.ergometrine
N
H

Imidazole N

e.g. pilocarpine

Purine 6 H
7
e.g. caffeine 1 N 5 N
8
2 N
N 4 9
3
Purine
Steroidal
e.g. Solanum and Veratrum
alkaloids

Terpenoid
e.g. Taxol
PHYSICAL-PROPERTY

I) They are colorless, crystalline solid. Exception - Berberin (Yellow),

Nicotine Coniine (liquid).

II) They are insoluble in water (exception liquid alkaloids soluble in water),

soluble in organic solvent ( CHCl3, Ethyl alcohol ether)

III) Taste: They are bitter in taste.

IV) Optically active, Most of levo ratatory but few are -Dextro rotatory e.g.

Coniine, some inactive- e.g.- papaverine.

CHEMICAL TEST OF ALKALOIDS

1. Mayer's Test:
Specimen with Mayer's reagent give Cream or pale yellow ppt.

2. Dragendroff Reagent Test:

Specimen with Dragendroff Reagent give orange ppt.

3. Wagners Test:
Specimen with Wagner's Reagent give brown or reddish brown ppt.

4. Hager's Test:
pecimen with Hager's reagent give yellow ppt. (Special Type)
5. Amonium Rinker Test:
Specimen with Ammonium Rinket solutions with HCL give flocculent pink
ppt.
Flavonoids
CONTENTS

➢ Introduction
➢ Structure of Flavonoids
➢ Classification and Chemistry of Flavonoids
➢ Sources of Flavonoids
➢ Biosynthetic Pathway of Flavonoids
➢ Role of Flavonoids in Plants
 ▪ Introduction
➢ Flavonoids are a group of plant polyphenolic secondary
metabolites showing a common three ring structure (Wiley J.
& Sons, Inc., Publication, 2010).

➢ Widely distributed in different amounts, according to the plant

species, organ, developmental stage and growth conditions.

➢ The Flavonoids have aroused considerable interest recently

because of their potential beneficial effects on human health
as well as their role in plant metabolism.

➢ They have been reported to have antiviral, antitumor, anti-

allergic, anti-platelet, anti-inflammatory and antioxidant
activities.
 ▪ Structure of Flavonoids

➢ Their basic structure is a skeleton of diphenylpropane,

namely, two benzene rings (ring A and B, see figure) linked
by a three carbon chain that forms a closed pyran ring
(heterocyclic ring containing oxygen,the C ring) with
benzenic A ring.

➢ Therefore, their structure is also referred to as C6-C3-C6.

In most cases, B ring is attached to position 2 of C ring, but it
can also bind in position 3 or 4; this, together with the
structural features of the ring B and the patterns of
glycosylation and hydroxylation of the three rings, makes the
flavonoids one of the larger and more diversified groups of
phytochemicals.
▪ Classification and Chemistry of
Flavonoids.
Flavonoids are classified in 6 major subgroups depending on the
carbon of the C ring on which B ring is attached, and the degree
of unsaturation and oxidation of the C ring.
B ring is linked in position
3 of the ring C-
isoflavones.

B ring is linked in position

4,
Neoflavonoids.

B ring is linked in position

2,
flavones, flavonols,
flavanones,
flavanols,catechin,
and anthocyanidin.

open C ring –
Chalcone

Wiley J. & Sons, Inc., Publication, 2010)

 Isoflavonoids Chalcones
Flavonol

SOURCES OF
FLAVONOIDS
Anthocyanins Flavone
Flavanone
 Classification of Flavonoids

➢ Class: Flavone

➢ Structure:

➢ Subclasses:
Apigenin
Luteolin
Tangeritin
Diosmetin

➢ Sources:
Celery, Parsley, Red Pepper, Ginkgo
biloba.
➢ Class: Flavonol

➢ Structure:

➢ Subclasses:
Kaempferol
Rutin
Myrecetin
Quercetin
Morin

➢ Sources:
Yellow Onions, scallions, broccoli,
Apple, berries.
➢ Class: Flavanone

➢ Structure:

➢ Subclasses:
Naringin
Naringenin
Hesperitin
Eriodictiyol

➢ Sources:
Oranges, Lemons, Grapes
➢ Class: Anthocyanin

➢ Structure:

➢ Subclasses:
Cyanidin
Malvidin
Pelargonidin
Peonidin
Delphinidin

➢ Sources:
Blue-berries, plum, brinjal, grapes
➢ Class: Isoflavonoids

➢ Structure:

➢ Subclasses:
Genistin
Daidzin
Glyceitin

➢ Sources:
Soyabean, soy foods, legumes
➢ Class: Chalcone

➢ Structure:

➢ Subclasses:
Phloretin
Arbutin
Chalchonaringenin

➢ Sources:
Tomatoes, pears, strawberry, wheat
products
 ▪ Role Of Flavonoids In Plant Defense

➢ Phenylpropanoids, act as key chemical modulators of plant

communication with insects and microbes, either as attractants or
repellants , or as phytoalexins against pathogens and herbivores.

➢ Derivatives of the initial phenylpropanoid scaffold play vital roles

in plant structural integrity, protection against UV radiation and
phytopathogens, internal regulation of plant cell physiology and
signaling. (Koes et al 1994, Shirley, 1996)

➢ Induce root nodulation when excreted by symbiotic nitrogen-fixing

rhizhobia (Mandal et al;2010).

➢ Some flavonoids provide stress protection, for example act as

scavengers of free radicals such as reactive oxygen species (ROS), as
well as metal chelating agents that generate ROS. (Mol et al., 1998;
Winkel-Shirley, 2002; Bradshaw and Schemske, 2003)
 ▪ Beneficial effects associated with
consumption of Flavonoids
➢ Reduced risk of cardiovascular diseases.

➢ Reduction in Blood Pressure due to its vasodilatory effect.

➢ Delays or prevents the onset of diseases caused by free

radicals

➢ Best antioxidant

➢ Anti-inflammatory activity

➢ Improvement of endothelial functions

➢ Inhibits LDL oxidation by free radicals

➢ Inhibits platelet Aggregation

➢ Antiviral

➢ Antibacterial
GLYCOSIDES

Introduction: No of medicinal plants containing organic constituents in conjugation with a

sugar moiety .It can be 1or2 .such compounds are called as glycosides. They exert
therapeutically significant effect on human and animals .Traditionally used in modern medicine
because of their cardio tonic, purgative, analgesic, anti-arrhythmic, demulcent action.

Defination:-glycosides are define as organic compound from plants and animal source, which on
enzymatic hydrolysis gives one or more sugar moieties along with anon sugar moiety. Sugar
moiety is called glycon and non sugar moiety is called aglycon or genin.

CLASSIFICATION:-
1) BASED ON THE CHEMICAL NATURE OF NON SUGAR MOIETY :-

• Anthraquinone glycoside : - anthraquinone moiety as aglycon . Ex: senna

• Sterol or cardiac glycoside: - aglycon portion is steroid molecule. Ex: digitalis
• Saponine glycoside
• Cyanogentic glycoside Ex : white cherry bark
• Isothiocynate glycoside Ex: black mustard.
• Flavonoid glycoside Ex : rutra graveolens, citrus bio flavonoid
• Coumarin glycoside or furano coumarine glycoside:- Ex : celery fruit
• Aldehyde glycoside Ex: vanilla pods
• Phenol glycoside Ex salcive
• Steroidal glycoside
• Glucosidal bitter or miscellaneous glycoside Ex salix species

2) BASED ON TE NATURE OF SUGAR MOITY:-

• Glucoside : sugar portion is glucose

• Rhamnoside : sugar portion is rhamnose
• Pentoside sugar portion is pentose
• Fructoside sugar portion is fructose
• Arabinoside sugar portion is arabinose

3) BASED ON LINKAGE BETWEEN GLYCON AND AGLYCON PORTION:-

OH groups reacting with any of the following medicates like, OH, CN, SH, NH product in
aglycon part
a) C-glycoside:-
Glycon-OH + HC –aglycon --> glycone-c-aglycon +H2O
Some of the anthraquinone glycoside like cascaroside in cascara, aloin in aloes shows the
particular linkage.
C-glycosides are called aloin type glycoside present in aloes. They do not hydrolyzed by heating
with dil acid or alkalis but by oxidative hydrolysis with Fecl3. cochical contains c-glycoside in
the form of coloring matter called carminoic acid
 b) O-glycoside
They are common in higher in plants Ex senna, rhubarb
They are hydrolyzed by treatment wit acid or alkali into glycon and aglycon portion.
c) S-glycoside
They occurrence of this glycoside is restricted to isothiacyanate glycoside like sinigirin in black
mustard formed by the condensation of sulphohydryl group aglycon to OH group of glycon.
d) N-glycoside
They most typical representation of this is nucleoside where the amino group reacts with OH
group of ribose or deoxyribose resulting into N-glycoside
4) BASED ON THERAPEUTIC NATURE OF GLYCOSIDE:-

• Cardiac glycoside Ex : Digitalis

• laxative glycoside Ex : Senna
• Anti-ulcer glycoside Ex : Liquorice
• Bitter glycoside Ex : quassia wood

GENERAL CHARACTERISTICS
1) Glycoside contains sugar but still the physical, chemical and therapeutic activity is based on
aglycon portion. Sugar facilitates the absorption of the glycoside .helping it to reach the site of
action
2) Glycoside are crystalline, amorphous substance which are soluble in water, and dilute alcohol
but in soluble in the CHCl3 and ether. The aglycon moiety is insoluble in non polar solvent like
C6H6
3) Glycosides are easily hydrolyzed by mineral acids, water and enzyme. They show optical
activity normally they are levorotatory
4) Glycoside can not reduce fehling’s solution until they are hydrolyzed
5) They are believed to facilitates growth and protection of plant
ISOLATION OF GLYCOSIDE
The method by which glycoside are isolated is called stas-otto method. The drug containing
glycoside is finely powdered and subjected to successive extraction in a soxhlet apparatus with
alcohol or suitable solvent.
During this method at first take drug containing glycoside, finely powdered that, and it is
extracted with alcohol or water by using soxhlet apparatus. After extraction, collect the extract
and treat with lead acetate to precipitate tannins after that filter it and to the filtrate pass H2S gas,
no lead acetate the precipitate as lead sulphide as this is toxic. Now after the extract again filter.
The filtrate is subjected to fractional crystallization, distillation or chromatography gives pure
component and the extract molecular structure is determined by the spectrophotometer, Ultra
Red assays, Infra red , NMR and mass spectroscopy etc.
Cardiac Glycosides
Cardiac glycosides are a class of organic compounds that increase the output force of the heart and
increase its rate of contractions by acting on the cellular sodium-potassium ATPase pump. Their
beneficial medical uses are as treatments for congestive heart failure and cardiac arrhythmias; however,
their relative toxicity prevents them from being widely used.[2] Most commonly found as secondary
metabolites in several plants such as foxglove plants, these compounds nevertheless have a diverse
range of biochemical effects regarding cardiac cell function and have also been suggested for use in
cancer treatment.

General structure

The general structure of a cardiac glycoside consists of a steroid molecule attached to a sugar (glycoside)
and an R group.[4] The steroid nucleus consists of four fused rings to which other functional groups such
as methyl, hydroxyl, and aldehyde groups can be attached to influence the overall molecule's biological
activity.[4] Cardiac glycosides also vary in the groups attached at either end of the steroid. Specifically,
different sugar groups attached at the sugar end of the steroid can alter the molecule's solubility and
kinetics; however, the lactone moiety at the R group end only serves a structural function.[5]

In particular, the structure of the ring attached at the R end of the molecule allows it to be classified as
either a cardenolide or bufadienolide. Cardenolides differ from bufadienolides due to the presence of an
“enolide,” a five-membered ring with a single double bond, at the lactone end. Bufadienolides, on the
other hand, contain a “dienolide,” a six-membered ring with two double bonds, at the lactone
end.[5] While compounds of both groups can be used to influence the cardiac output of the heart,
cardenolides are more commonly used medicinally, primarily due to the widespread availability of the
plants from which they are derived.

Classification

Cardiac glycosides can be more specifically categorized based on the plant they are derived from, as in
the following list. For example, cardenolides have been primarily derived from the foxglove
plants Digitalis purpurea and Digitalis lanata, while bufadienolides have been derived from the venom
of the cane toad Bufo marinus, from which they receive the “bufo” portion of their name.[6] Below is a
list of organisms from which cardiac glycosides can be derived.
Plants from which cardenolides can be derived[edit]

• Convallaria majalis (Lily of the Valley): convallotoxin[7]

• Antiaris toxicaria (upas tree): antiarin

• Strophanthus kombe (Strophanthus vine): ouabain (g-strophanthin) and other strophanthins

• Digitalis lanata and Digitalis purpurea (Woolly and purple foxglove): digoxin, digitoxin

• Nerium oleander (oleander tree): oleandrin

• Asclepias sp. (milkweed): oleandrin

• Adonis vernalis (Spring pheasant's eye): adonitoxin

• Kalanchoe daigremontiana and other Kalanchoe species

Organisms from which bufadienolides can be derived[edit]

• Leonurus cardiaca (motherwort): scillarenin[7]

• Drimia maritima (squill): proscillaridine A

• Bufo marinus (cane toad): various bufadienolides

• Kalanchoe daigremontiana and other Kalanchoe species: daigremontianin and others

Chemical test-
Killer killiani test: Glycoside is dissolved in a mixture of 1 % ferric sulphate solution in (5%) glacial acetic
acid. Add one or two drop of concentrated sulphuric acid. A blue colour develops due to the presence of
deoxy sugar.

Raymond’s test:

To the drug, add a few ml of 50% ethanol and 0.1 ml of 1 % solution of m- dinitrobenzene in ethanol.
To this solution, add 2-3 drops of 20% sodium hydroxide solution. Violet colors appears, this is due to
presence of active methylene group.

Legal test:

To the drug add few ml of Pyridine and 2 drops of Nitroprusside and a drop of 20% NaOH solution. A
deep red colour is produced.

Baljet test:

Take a piece of lamina or thick section of the leaf and add sodium picrate reagent. If glycoside is
present yellow to orange colour will be seen.

Anthraquinone glycosides

The anthraquinone glycosides are the ones whose aglycone component is a

polyhydroxyanthraquinone derivative. The drugs having these glycosides possess cathartic activity.
The polyhydroxyanthraquinone derivatives present in these drugs are chrysophanic acid (1, 8-
dihydroxy- 3- methylanthraquinone), aloe emodin (1, 8- dihydroxy-3- methyl anthraquinone),
Frangula emodin and rhein (1, 8- dihydroxy anthraquinone -3-carboxylic acid).

Glycosides of anthranol and anthrones, reduced derivatives of anthraquinones, also occurs in the
plant materials, and they make significant contributions to the therapeutic action of these natural
products. The free anthraquinone aglycones exhibit little therapeutic activity.

The sugar residue facilitates absorption and translocation of the aglycone to the site of action. The
anthraquinone and related glycosides are stimulant cathartics and exert their action by increasing the
tone of the smooth muscle in wall of the large intestine.

Glycosides of anthranol and anthrones elicit a more drastic action than the corresponding
anthraquinone glycosides and a preponderance of the former constituents in the glycosidic mixture
can cause discomforting griping action.
Chemical Test:

1. Borntranger’s test:

Powdered leaves of Senna are boiled with dilute sulphuric acid. Filtered and cooled. The
filtrate is extracted with chloroform or benzene and dilute ammonia is added to it. The
ammonical layer becomes pink to red due to the presence of anthraquinones derivative.
 2. Modified anthraquinone test-
Take 0.1 gm of drug and add 5ml of 5% solution of ferric chloride and 5ml dilute
hydrochloric acid and heat on boiling water-bath for 5 minutes, cool the solution and
shake gently with an organic solvent like benzene. Separate the organic solvent layer
and add an equal volume of dilute ammonia. A pinkish red colour is formed in
ammonical layer. This test is of C. glycoside.

Saponin glycosides

Saponin Glycosides are the plant glycosides possessing a distinct property of forming soapy lather in
water. Therefore, they are largely used as detergents. Saponins on hydrolysis give sugars (glucose,
galactose, rhamnose or xylose, etc.) and aglycones (sapogenin). Chemically, sapogenins are
characterized by the presence of a spiroketal side-chain. Saponins have also been used in medicine,
foaming agents, in fire extinguishers and fish poisons.

Fishers are killed by introducing sapogenins in water but they are not rendered inedible because the
saponins is not toxic to human being when given orally (of course it is poisonous if used intravenously
because under such conditions it causes haemolysis).

Properties of saponin glycosides:

Saponins are mostly amorphous in nature, soluble in alcohol and water, but insoluble in non-polar
organic solvents like benzene, n-hexane, etc.

Saponins also possess certain special properties:

1. An aqueous solution froths when shaken.

2. An aqueous solution absorbs and retains in solution a volume of gas (e.g. carbon dioxide) several
times greater than that absorbed by an equal volume of water.

3. An aqueous solution, shaken with oil and fats, produces emulsion, which stable for a short time,
varying from a few minutes to an hour or more. Emulsification is caused by the saponin lowering the
surface tension between the oil and the water.

4. An aqueous solution added to red blood corpuscles causes haemolysis, e.g. disintegration and
solution of the corpuscles to form a clear red liquid.

Classification of Saponins:

They are classifying in two groups:

I. Tetracyclic triterpenoid spaonins:

(a) Dioscorea bark- Diosgenin

(b) Solanum Berries- Solasodine

(c) Asparagus roots- Sarsapogenin

II. Pentacyclic Triterpenoid saponins

(a) Ginseng- Gingenoside

(b) Licorice- Glycyrrhizin

(c) Senega- Senegin- II

(d) Quillaja – Quillaia

(e) Sarsaparilla- Sarsapogenin

Chemical tests for saponin glycosides:

1. Foam test:

Shake the drug extract or dry powder vigorously with water. Persistent foam observed.

2. Haemolytic test:

Add drug extract or dry powder to one drop of blood placed on glass slide. Haemolytic zone appears.
Resins
These are amorphous products of complex chemical nature. These are amorphous mixtures of
essential oils, oxygenated products of terpenes and carboxylic acids. These are found as
exudation from the trunk of various trees.

Properties-

1. These are transparent or translucent solids, semisolids or liquid substances containing

large number of carbon atoms.
2. On heating they are softened and then melted if in solid form.
3. They are practically insoluble in water but dissolve in organic solvents like alcohol, ether
and chloroform. Also soluble in volatile and fixed oils.
4. They are hard, electrically non-conductive and combustible masses.
5. They produce smoky flame on burning.
6. They are usually formed in schizogenous or schizolysogenous cavities of ducts as end
products of metabolism.

Classification-

Chemically resins contain organic acids, alcohols, esters and neutral resins. Depending upon the
type of constituents present, resins are classified as-

1. Resin acids- These are mixture of oxy acids, carboxylic acids and phenolic acids. They
are present in free state or as esters. They are soluble in aqueous alkaline solution which
form soap like froth on shaking. Ex- Abietic acid in colophony resin, Copaivic acid and
Oxycopaivic acid in Copaiba, Guaiconic acid in Guiac resin.
2. Resin alcohols- These are complex molecules with high molecular weight. They are
present in either free state or as esters of simple aromatic acids ex benzoic acid, Salicylic
acid and Cinnamic acid. Resin alcohols are further divided into resinotannols and
resinols. Resinotannols are tannins and form blue colour with ferric chloride. Ex. Aloe
resinotannol from aloe, Suma resinotannol from Benzoin. Resinols does not contain
tannins. Ex. Benzoresinol from Benzoin, Storesinol from storex.
3. Resenes- they are complex neutral compound which do not respond to any chemical
reaction. They are insoluble in acids and alcohols and do not form any salt and not get
hydrolysed. Ex. Asafoetida, Colophony, Dammar.

Classification on the basis of their occurrence in combination with other compounds-

a. Oleoresin- Resins and oils in homogenous mixtures. Ex. Copaiba capsicum, Canada
balsam.
b. Oleogumresin- Homogenous mixture of oil, gum and resin. Ex. Myrrh, Guggul,
Asafoetida.
 c. Glycoresins- Mixture of resins with sugar. Ex. Jalap, Ipomoea
d. Balsams- If resin contains benzoic acid or cinnamic acid. Ex. Balsam of tolu, Balsam of
Peru, Storex

Extraction and isolation-

Pharmaceutical resins are obtained from plants and animals by one of the following methods-

a. By extraction with alcohol and precipitation with water.

b. By distillation for separation of oil.
c. By heating the plant part.
d. As plant exudates by incision.
e. By collecting fossil resins.

Identification tests-

1. The alcoholic solutions of resins are acidic in nature.

2. When treated with concentrate sulphuric acid, bright red colour obtained.
3. With water, emulsion is formed.
4. With concentrate nitric acid, resins give green colour.
5. When resins are heated, cooled and examined under microscope, crystals of cinnamic
acids are shown.
6. When treated with ammonia solution and examined under UV- Blue fluorescence
observed.

Uses-

 Carminative and stimulant (Ginger, Asafoetida)

 Antiseptic (Benzoin, Tolu balsam)
 Expectorant (Tolu balsam)
 Flavoring species (Ginger, Turmeric)
 Diuretic (Benzoin)
 Industrial uses- as perfumes, chewing gum and confectionary preparation
Tannins
These are complex organic, non-nitrogenous phenolic compounds of high molecular weight and
posses the property to tan i. e. convert hide and skin into leather. The term tannin was first
applied by Seguin in 1796. These are detected qualitatively by a tanning test (the gold beater’s
skin test) in determined quantitatively by its absorption on standard hide powder.

Occurrence- these are widely distributed in plant kingdom, in almost every plant family. When
tannins occur in appreciable quantity, they are usually localized in specific plant parts such as
leaves, fruits, barks and stems. Although often found in immature fruits, tannins usually
disappear during the ripening process. In plant metabolism, tannins probably serve as protective
during certain stages of growth and finally they are destroyed or deposited as end products of
metabolism in certain dead tissues to the mature plant (outer bark, hard wood).

Chemically tannins contain the mixture of complex organic substances in which polyphenols are
present, generally with ortho dihydroxy or ortho trihydroxy groups on a phenyl ring.

Classification- On the basis of chemical nature-

1. Hydrolysable tannins- These tannins can be readily hydrolysed by acids, alkali or

enzymes to yield phenolic acids and sugar. The products of hydrolysis are Gallic acid,
Ellagic acid, so also known as gallic acid tannins. These produce dark blue to black
colour with ferric chloride solution but are not precipitated with bromine water. Ex.
Harde (Myrobalan), Bahera, Amla, Rhubarb, Chestnut, red rose petal, Pomegranate rind
and bark.
2. Condensed/ Non-hydrolysable tannins- These are resistant to hydrolysis or cleavage.
They are related to flavonoid pigments, because they are formed via derivatives of
flavones like catichin. When heated with enzymes or mineral acids, they are polymerized
or decomposed into red coloured water insoluble compound known as Phlobaphenes.
These give green colour with Ferric chloride and precipitated with bromine water. Ex.
Ashoka bark, Pale catechu, Black catechu, Pterocarpus.
3. Pseudotannins- They are phenolic compounds of low molecular weight and they do not
show the gold beaters skin test. They occur as gallic acid in rhubarb, catechin on cocoa,
chlorogenic acid in coffee and nux vomica.

Properties-

1. They are amorphous in nature and form colloidal solution with water and re
noncrystalline.
2. These are mixture of complex organic substances in which polyphenols are present,
generally with ortho dihydroxy or ortho trihydroxy groups on a phenyl ring.
3. High molecular weight and not contain nitrogen atom.
4. Show acidic reaction due to phenol in soluble form.
 5. Soluble in alcohol, glycerine and dil alkali but practically insoluble in organic solvents
except acetone, sparingly soluble in chloroform and ethyl acetate. Phlobaphenes are
soluble in alcohol but practically insoluble in water.
6. They precipitate proteins from solution and are able to combine with them rendering
them resistant to proteolytic enzymes. This property is known as astringent action and
many tannins containing drugs are used as astringent medicinally.
7. Have sharp puckering (Astringent/ acidic) taste.

Chemical tests-

Small quantity of alcoholic or aqueous extracts are taken nd following tests are performed-

1. Gelatin test:

To a solution of tannin, aqueous solution of gelatin and sodium chloride are added. A white buff
coloured precipitate is formed.

2. Goldbeater’s skin test:

A small piece of goldbeater skin (membrane prepared from the intestine of an ox) is soaked in
20% hydrochloric acid, ringed 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 solution of ferrous sulphate.
A brown or black colour is produced on the skin due presence of tannins.

3. Phenazone test:

A mixture of aqueous extract of a drug and sodium acid phosphate is heated and cooled and
filtered. A solution of phenazone is added to the filtrate. A bulky coloured precipitate is formed.

4. Match stick test (Catechin test):

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.

5. Chlorogenic acid test:

An extract of chlorogenic acid containing drug is treated with aqueous ammonia. A green colour
is formed on exposure to air.

6. Vanillin-hydrochloric acid test:

Sample solution and added vanillin- hydrochloric acid reagent (Vanillin 1 gm, alcohol 10 ml,
concentrated hydrochloric acid 10 ml). A pink or red colour is formed due to formation of
phloroglucinol.
 7. Solution of tannin precipitates gelatin and alkaloid.
8. They form dark blue or green blac soluble compound with ferric chloride solution.

Extraction and isolation-

Hydrolysable tannins- Plant twigs are extracted with a mixture of ether and alcohol (4:1). To
the extract water is added. Alcoholic aq extract separated from ether layer. Ether layer on
evaporation gives gallic acid and aq alcoholic layer on evaporation gives tannic acid. Both are
isolated by fractional distillation or chromatography.

Condensed tannins- Leaves and twigs are put into a large pan with full of boiling water. Boiled
for 3 hours and stirred well. Then leaves and twigs are separated from extract by decantation.
Marc is pressed and the expressed extract is combined with above decanted extract. It was
evaporated till it become thick mass, then cool with stirring. Semisolid mass produced which is
further purified by fractional distillation or chromatography.

Uses-

 Used in the tanning process of animal hides to convert them into leather.
 Aqueous solution is used to precipitate gelatin, protein and alkaloids in laboratory.
 As healing agents in inflammation, leucorrhoea, gonorrhea, burns, piles and diarrhea.
 Used as antidote in treatment of alkaloid poisoning.
 These form deep red coloured complex with iron salts that is used in manufacturing of
inks.
 Antiseptic effect on mucous membrane and skin due to phenolic compounds.
 As astringent
Terpenoids

It represents hydrocarbons as well as their oxygenated derivatives and also regarded as

derivatives of polymer of Isoprene (C5H8)n.

Isoprene unit-

2-methyl-1,3-butadiene

These units are joined by Head to tail, it is called as Isoprene rule. These are widely distributed
in plant kingdom.

Occurrence- These are mainly found in essential oils which have pleasant odour and present in
almost all parts of a plant.

Classification-

1. Depending on the number of Isoprene unit-

S. No. Name of class Number of Formula Example
units
1. Hemiterpene/ 1 C5H8 Not found in
Isoprene nature
2. Monoterpene 2 C10H16 Geraniol,
Menthol
3. Sesquiterpene 3 C15H24 Zingiberene
4. Diterpene 4 C20H32 Phytol, Vitamin
A
5. Sesterpenes 5 C25H40 Cybastacines
A, B
6. Triterpenes 6 C30H48 Squalene
7. Tetraperpenes/ 8 C40H56 Alpha and Beta
Carotenoids carotene
8. Polyterpene/ Rubber n (C5H8)n Rubber
2. On the basis of number of rings present in structure
A. Acyclic terpene- No ring in structure- Myrcene
B. Monocyclic- one ring- Limonene
C. Bicyclic- Two ring- Abietic acid
D. Tri…, tetra…, pentacyclic..
Volatile oils-

The odorous volatile principle of plants and animals sources are known as volatile oils. They
evaporate when exposed to air at ordinary room temperature, so also called as ethereal oils. They
represent essence or active constituents of plant so called as essential oils. Chemically they are
derived from terpenes and their oxygenated derivatives and generally made up of mono, sesqui
and diterpenes.

Properties-

1. Soluble in alcohol, ether, and lipid solvents and insoluble in water.

2. Generally lighter than water.
3. They have characteristic odour and high refractive index
4. Optically active compounds.
5. They are secreted in special structures such as ducts, cells, trichomes and Lysigenous
glands.
6. Commonly found in dicot plant families such as Umbelliferae, Labiatae, Zingiberaceae
etc and present in entire plant or any part of plant.

Isolation-

1. By Hydrodistillation- It includes water distillation, water and steam distillation & steam
distillation used for extraction of volatile oil from herbal drugs. The fresh crude drug is
subjected to hydrodistillation for volatile oil isolation. The apparatus used is Clevenger
apparatus.
2. Enfluerage method- It is used for extraction of delicate perfumes. For this fresh flower
petals are mechanically spread on fatty material layer. It was allowed to imbibe and the
exhausted petals are replaced with fresh petals. The process is continued till the fatty
material layer is saturated with volatile oil which is further extracted with lipid solvents.
3. Ecuelle method- it is used for extraction of citrus oils. In this the oil cells are ruptured
mechanically using pointed projections by twisting raw material over them in clockwise
direction either mechanically or manually.
4. By using liquid Carbondioxide- CO2 is liquefied under pressure and it act as solvent for
extraction of essential oils. It reverse back to gaseous nature when pressure is reduced
and leaving no any residue of solvent.
5. Sfumatrice method- It is a cold expression method of volatile oil isolation from Citrus
fruits. The equipment consist of a metallic chain that is drawn by two horizontal ribbed
rollers. The peels are passed through these rollers and pressed and bent to release their
oil. This oil is then washed, separated, centrifuged and purified.
6. Cohobation method- It is a procedure that can only be used during water distillation or
water & steam distillation. In this, the distilled water returns to the distillation flask after
 the oil has been separated from it, so that it can be re-boiled. The principal behind it is to
minimize the loss of oxygenated compounds which dissolve in the distilled water.

Types of volatile oils- On the basis of chemical nature-

1. Aldehyde volatile oil- Cinnamon, Lemon peel

2. Alcohol V. O.- Cardamom, Coriander
3. Ester VO- Mustard
4. Hydrocarbon VO- Turpentine
5. Ketone VO- Camphor, Musk
6. Phenolic VO- Clove

Chemical tests-

A. A thin section of drug treated with alcoholic solution of Sudan-III- gives red colour.
B. A thin section of drug treated with a drop of tincture alkane- gives red colour.

Storage- Volatile oils should be stored properly in well closed well filled amber colour
containers away from light and in cool place.

Uses-

1. As flavouring and perfuming agents.

2. For medicinal uses like- Carminative (Cardamom), anthelmintic (Chenopodium), Local
anaesthetic (Clove), Antiseptic (Eucalyptus) etc.
3. Citral is obtained from Lemon grass oil and Citral is used for synthesis of vitamin A.
4. Terpeneless volatile oils are used for high priced perfumes because of their specificity
and stability. These are prepared by removing hydrocarbons and undesired components
by fractional distillation.