CHEMICAL NATURE OF NATURAL

DRUGS
UNIT 8
1) ALKALOIDS
2) TERPENOIDS
3) GLYCOSIDES
4) VOLATILE OILS
5) LIPIDS: OILS, FATS AND WAXES
6) TANNINS
7) RESIN AND RESIN COMBINATION
8) CARBOHYDRATES
9) PESTICIDES OF NATURAL ORIGEN
 1. ALKALOIDS

“Alkaloids are basic nitrogenous organic

products of the plant origin, having marked
physiological action when administrated orally
or internally ”
1st alkaloid discovered by Derosene in 1803
(Narcotin)
Sertuerner in 1806 laid the foundation of
alkaloid chemistry
Occurrence & Distribution of Alkaloids
• They are occur in various parts of plant like
fruits (black pepper, opium), seeds (nux
vomica), leaves (Dhatura, belladonna) and
barks (cinchona), stem (ephedra).
• Mainly alkaloids are obtained from
angiosperm plants belonging to family like
Leguminosae, Papaverace, Ranunucleaceae,
Rubiaceae, Beberidaceae and Liliacae
 Properties of Alkaloids
• Alkaloids are colorless (Berberine are coloured), crystalline,
non volatile & bitter solids
• Most of them are optically active(plane polarized light) and
are laevorotatory (left).
• Insoluble or sparingly (polar/salt) soluble in water
• Soluble in organic solvents (non polar/base) like alcohols,
ether etc,
• Bitter taste
• highly potent medicament & possess curative properties.
• Alkaloids in high does in poisonous.
• C H O with nitrogenous atom (1 or more N)
• Heterocyclic or non heterocyclic form +nt
 Function of Alkaloids
• Protective agents
• Plant stimulants.
• Physiological activity regulators
• De-toxicating agents
• Reservoir of protein synthesis
 Identification test for Alkaloids
A. Identification by precipitation method,
1. Mayer’s reagents (potassium mercuric iodide solution):
cream or pale yellow PPt
2. Dragendroff’s reagents (potassium bismuth iodide
solution): brown or reddish brown color or ppt.
3. Wagner’s reagent (iodine & potassium iodide solution);
brown or reddish brown color ppt.
4. Hager;’s reagent (saturated solution of picric acid); yellow
ppt.
B. Identification by color reagents.
e.g. potassium chloride with caffeine
Mineral acid with colchicine
 Classification of Alkaloids on the bases of
chemical structure
Sr. no Type of alkaloids Examples source
1 Quinoline Alkaloids Quinine, Quinidine cinchona
cinchonine
2 Alkaloidal amnes Ephedrine, colchicine Ephedra, colshicum
3 Isoquiniline Alkaloids Papaverine, narcotine Opium,
ipecacuanha
4 Indole Alkaloids Strychnine, Nux-vomica, ergot
ergometrine, reserpine
5 Imidazole Alkaloids Pilocarpine pilocarpus
6 Phenanthrene Alkaloids Morphine, codenine opium
7 Purine Alkaloids Caffeine, theobromine Tea, coffee
8 Pyrrol & pyrolidine Alkaloids Nicotine, hygrine Tobacco, coca
Sr. no Type of alkaloids Examples source

9 Pyridine & piperidine alkaloids Ricinine, lobeline Castor, lobelia

10 Steroidal alkaloids Solanin, solanidine Potato, kurchi

11 Tropane alkaloids Atropine, hyoscine datura,

hyoscyamus

12 Diterpene alkaloids Acinine, aconitine aconite

 Extraction
Drug ( moisture H2O)

treat with lime

Extracted with organic solvent
( chloroform, benzene ) filtrate
1. aq. layer, (rejected)
2. organic layer (alkaloid)
treat with (Acid, H2o)

Salt form

1. Aq. Layer (pure alkaloid salt separate by using TLC, and different
Chromatography teq.)
2. Organic layer(rejected)
 2. TERPENOIDS
• Terpenes (phytoconstituents) can be define as
natural products containing numbers of
isoprene (C5H8) unit.
• Terpenoids include hydrocarbons, as well as
their oxygenated derivatives.
 Properties of Terpenoids
• Colorless liquid or solids having pleasant
smell.
• Insoluble in water
• Soluble in alcohol, organic solvent
• Most of them are optically active
• Oxidized by oxidizing agents
 Uses of Terpenoids
• As they are having pleasant odour, terpenoids
are used In perfumery, cosmetics and soap
industry
• Therapeutically they are used as Antiseptic,
carminatives, diuretics
• Analgesic aromatics, irritant etc.
• Also used as, insecticides, pesticides and
deodorants
 classification
Sr. no Name of class of No of isoprene
terpenoids units
1 Isoprene
2 Monoterpenes
3 Sesquiterpenes
4 Diterpenes
5 Triterpenes
6 Tetraterpenes
7 Pentaterpenes
8 polyterpenes
Molecular formula
1 C5H8
2 C10H16
3 C15H24
4 C20H32
6 C30H48
8 C40H64
9 C50H80
n (C5H8)n
• Depending upon type and number of ring
reported in terpenoids, they are classified as;
1. Acyclic terpenoids-have open chain structure
2. Monocyclic terpenoids-have one ring in str.
3. Bi cyclic terpenoids-have two ring in stru.
4. Tri cyclic terpenoids- have three ring in str.
 3. Volatile oils
• The odorous & colorless principle of plants
and animals sources which are evaporated
when expose to air called as volatile oil.
• As they are evaporate when exposed to air at
ordinary temperature , they are also called
‘Ethereal oils.
• They represent essence, hence they are also
known as essential oils.
 Properties of Volatile oils
• Liquid in nature. But Camphor and menthol solid in
nature
• Soluble in alcohol, ether and other organic solvents
• Insoluble in water
• They are usually lighter than water
• They possess characterized by high refractive index
• Most of them are optically active.
• Chemically these are terpenes.
• They are made up of isoprene units (C5H8).
• Oxygenated derivative of hydrocarbens, order, test
 Occurrence &distribution volatile oils
• They are present either in entire plant or in
any part of plant. They are commonly found in
species of Labiatae, Rutaceae, Piperaceae,
Zingiberaceae, Myrtaceae
 Classification
l Types uses

1 Hydrocarbon volatile oils Turpentine, Black pepper

2 Alcohol volatile oils Cardamom, rose

3 Aldehyde volatile oils Cinnamon, lemon peel

4 Ester volatile oils Lavender, mustard

5 Ketone volatile oils Caraway, camphor

6 Phenol volatile oils Clove, thyme

7 Oxide volatile oils Eucalyptus, chenopodium

8 Phenol ether volatile oils Fennel nutmeg

 Chemical test for volatile oils
• To thin section of drug add alcoholic solution
of Sudan Red-III, red color indicate the
presence of volatile oil
• The thin section of drug add drop of tincture
of alkana, red color indicate the presence of
volatile oil.
 Isolation of volatile oils
• Volatile oil are extracted by following methods
1. Hydro-distillation.
2. Enfleurage method.
3. Ecucelle method
4. By liquid carbon dioxide
 1. Hydro-distillation:
• Method is comprises of water distillation,
steam distillation , water and steam
distillation is used for extraction of volatile oils
from herbal drugs. (Clevenger apparatus)
• Fresh leaf are extracted by water distillation,
while dried parts of plants are extracted by
steam distillation
 2. Enfleurage:
• This method is used for delicate perfume. The
fresh flower petals are mechanically spread on
layer of fatty materials, allowed to imbibe and
exhausted petal are replaced by fresh
materials.
• This process is continued till fatty layer is
saturated with volatile principles which are
than extracted (petrolium ether, evaporate)
with fatty solvents
 3. Ecuelle method
• This method is used for extraction of citrus oil,
lemon oil wherein oil cells in ring are ruptured
mechanically using pointed projection by
twisting raw material over them clockwise
direction either mechanically or manually
 4. Liquid Carbon Dioxide:
• Liquid carbon dioxide is also used to extracted
essential oils, when liquefied under pressure it
act as solvent, reversing back to gaseous
nature when pressure is reduced living no
residue of solvent.
 Uses:
• Used as flavoring and perfuming agents in
pharmaceutical formulation, food, beverages and
cosmetics.
• Carminative e.g. Cinnamon
• Antihelmintics e.g. Chenopodium
• Diuretic e.g. Juniper
• Antiseptic e.g. Eucalyptus, clove
• Spices e.g., clove cardamom
• Antimicrobial e.g. garlic
 4. GLYCOSIDES

▪ Glycoside are organic compound of plant and

animal origin which yield on either acidic or
enzymatic hydrolysis, one or more sugar and non
sugar residue.
Glycoside hydrolysis (acidic & enzymatic) Glycone + Aglycone
(Sugar) (None Sugar)
▪ The non-sugar moiety called as aglycone or genin.
▪ Sugar moiety called as glycones .
▪ E.g. Rhamnose , glucose, malose
 Properties of Glycosides
Physical Properties
▪ Glycosides are colorless (anthracene glycoside red,
flavonoid yellow), crystalline, and non reducing
compound, solid compound.
▪ Most of them are optically active, and are laevorotatory.
▪ They are water soluble as well as alcohol soluble.
▪ They are hydrolyzed with dilute acids & enzymes.
Chemical properties
▪ Condensation product of aglycone and glycone
▪ α-meythyl glycoside and β methyl glycoside are glycoside
are prepared synthetically
 Function of Glycosides

❑Protective agents
❑Plant stimulants
❑Growth regulators
 CLASSIFICATION

The glycosides can be classified by the

glycone, by the type of glycosidal linkage, and
by the aglycone.
 Classification of Glycoside in the basis of
Aglycone
• Glycosides are classified on the basis of chemical nature of their aglycone moieties as follows;
1. Cyanophoric glycoside: e.g. Amygdalin in bitter almond
2. Cardiac glycoside:
- Cardenolides (C 23): e.g. digitoxigenin in digitalis
- Bufadienolids (C 24): e.g. strophanthoside in strophanthus
1. Saponin glycoside:
- steroidal saponin e.g. Diosgenin in dioscovea, Gitonin
- Triterpenoid saponin e.g. glycyrriza
1. Isothiocynate glycoside: e.g. sinigerin in mustered
2. Phenolic glycoside
• Depending upon chemical structure phenolic glycosides are subdivided as follows:
a. Simple phenolic glycoside; e.g. salicin in salix
b. Anthracene glycoside; e.g. barbaloin in aloe
c. Coumarin glycoside; e.g. umbelliferon in asafoetids
d. Flavone & flavonoid glycosides; e.g. kaemferol in senna
e. Anthocyanidin glycosides; e.g cyanidin in rose
 Classification of Glycoside in the basis of Glycoside
linkage (Glycone)
❑ O-glycosides : in these glycosides the sugar part
is linked with alcoholic or phenolic hydroxyl or
carboxyl group of aglycone part. Eg rhen in aloe
❑ S-glycosides : in these glycosides the sugar
attached to a Sulfur atom of aglycone such as in
sinigrin in mustered .
❑ N-glycosides : in these glycosides the sugar
linked with Nitrogen atom of (-NH2,-NH-)amino
group of aglycone like in nucleosides DNA,RNA
❑ C-glycosides : in these glycosides the sugar linked
(condensed) directly to Carbon atom of aglycone
like in aloin.
 Chemical test for Glycosides
a) Cyanophoric glycosides
Take power in test tube, add little water and suspend
the piece of sodium picrate paper above the drug.
Allow for thirty minutes. Hydrocyanic acid gets
evolves and turns the picrate paper brick-red colour.
b) Saponin glycosides
- Shake powdered drug with water, formation of foam
indicate the presence of saponin. (Foam test)
- Aqueous solution of saponin containing drug, when
added to sample of blood caused haemolysis.
C) Cardiac glycoside (killer-killiani test)
❑ Boil about 1 gm of digitalis powder with 10 ml of 70% alcohol
for 3 minutes and filter it.
❑ To filtrate add 5 ml water & 0.5 ml strong lead acetate
solution and filter again. To filtrate add equal volume of
chloroform and evaporate(heat) to yield extract (residue).
❑ The extraction is dissolve in glacial acid and add 2 drop of
ferric chloride after cooling .
❑ These contents are transferred to a test tube containing 2 ml
of cone. Sulphuric acid.
❑ A reddish brown layer acquiring blush green color on standing
is observe due to presence of digitose at interface & pale
green color in upper layer due to presence or cardiac
glycoside.
 Isolation of Glycosides
▪ The finely powdered plant part is extracted with water or alcohol in
soxhlet apparatus. ( residue, filtrate)
▪ The enzymes present in plant tissue are destroyed by heating at
suitable temperature.
▪ Special care should be taken in case of thermo liable glycosides and
they should be extracted at low temperature.
▪ The non-glycosidal impurities (filtrate { crude glycoside, tenin
impurities}) are precipitate with lead acetate solution and excess of
latter is removed by passing hydrogen (H2S)supplied gas through
the extract. (Filtrate(Crude glucoside) +ppt)
▪ The concentration of extract gives crude glycoside, which is further
purified using suitable solvents and chromatography, according to
the chemical nature and properties of glycosides.
5. Resins and Resins Combinations

“HETEROGENOUS PLANTS EXTRACT OR

EXUDETES”
Resins are amorphous products of complex
chemical nature. These are amorphous
mixture of essential oil, oxygenated products
of terpenes and carboxylic acids found as
exudations from the trunk of various trees.
 Properties of Resins
▪ Non-crystallizable, transparent or translucent
solids, semi-solid or liquid substance containing
large number of carbon atom.
▪ Resins are heavier than water.
▪ Insoluble in water but soluble in alcohol, volatile
oils, fixed oil, chloral hydrate and non-polar
organic solvents like benzene or ether.
▪ When heated, they are soften and ultimately
melt.
▪ Chemically, they contain organic acids, alcohol,
esters and neutral resin.
 Classification of Resins
1. Acid resins; acid is main constituents of the
resins. E.g. Abiatic acid (colophony),
commiphoric acid (myrrh).
2. Ester resins: this group contains esters as chief
constituents of resin e.g. Benzyl Benzoate
(benzoin), ethyl cinnamate (Sotrax)
3. Resin Alcohol: The contents are the complex
alcohols of high molecular weight. They are
either in free state or as esters. e.g.
peruresunnotanol (peru balsam)
toluresinotannnol (tolubalasam)
 Distribution of Rasins
Roots: Zinger, Turmeric
Trunk: Tolu balasam
Flowering and fruiting tops: Cannabis
Fruits: Capsicum, Black paper
Seeds : Kaladana
 Resin combination
Homogenous combination of resin with other plant
products like volatile oil, gum etc. Are known as
resin combination
Classification of resin combination:
Oleo resin: (volatile oil+ resin) e.g. ginger, capsicum
etc
Oleo gum resin : (Volatiile oil+ gum + resin) e.g.
jalap, ipomoea
Balsam : benzoic acid+ cinnamic acid e.g.
tolubalasam, peru balasam
 Extraction or Isolation of resins
1. By simple extraction method e.g. jalap,
capsicum, ginger
2. By distillation method e.g. colophony
3. By heating method e.g. guaiacum
4. As plant exudates by incision e.g. myrrh,
asafoetida, balsams etc.
5. By collecting fossil resins e.g. copal, kauri etc
 Therapeutic Uses
• Antiseptic eg. Turmeric, benzoin
• Expectorants eg. Zinger, black paper
• Carminative eg. Asafoeitida, black paper
• Anticancer eg. podophylum
• Flavoring agents
• They are also used in perfumery
 Tannins
• Tannins are naturally occurring complex
organic compounds possessing nitrogen free
polyphenols of high molecular weight.
Or
• Tannins are the derivatives of polyhydroxy
benzoic acid capable of combination with
protein and causing precipitation.
• E.g. Black catechu and pale catechu
 Properties of Tannins
• Non-crystallisable,
• Alcohol and water soluble
• Causes precipitation of glycoside, protein and
alkaloids (astringent)
• When applied to smooth muscles, they cause
contraction.
 Classification of Tannins
1. Condensed tannins (non hydrolysable tannins): these
are the true tannins, which on acid or enzyme
treatment get decomposed into red insoluble
compounds known as phlobaphenes.E.g. kitonnic
acid, catechutannic acid and cinchotannic
2. Hydrolysable tannins: these are hydrolyzed by acid or
enzyme and produce gallic acid and ellagic acid.
Chemically these are esters of phenolic acid like gallic
acid and ellagic acid e.g. gallic acid- gallotannins (
rubarb, colve) ellagic acid – ellagitannins ( pomegrate
bark)
 Chemical test

1. Test with ferric chloride: with ferric chloride solution, hydrolysable

tannin gives blue-black colour and condensed tannins gives
brownish-green tint
2. Gold beater skin test: a piece of gold beater skin, when treated
with dilute hydrochloric acid ferrous sulphate and test solution of
tannin gives brown or black colour
3. Gelatin test: with gelatin solution (p) (1%) containg sodium
chloride (10 %) tannins are precipitated out from the solution
4. Match stick test: dip the match stick in an extract of drug and
moisten with conc. HCl and warm over a flame. Match stick turn
pinkish purple.
5. Vanillin hydrochoric acid test: tannins gives pink colour with
vanillin hydrochloric acid solution.
 Isolation of tannins
Power drug sample extract with alcohol
filter filtrate addition of water
shake two layer-1. organic
phase(impurities) 2. aq. Phase (tannins) crude
tannins alcohol sol. Addition tannin ppt (pure
form)
 uses
• Antiseptic: catechu, Amla
• Laxative: Amla
• Industrial uses: lather industry, printing
industry