Secondary Plant Metabolites

(Active Constituents)
• The secondary metabolites act as a protective
agents.
• They constitute as the waste product of
metabolism (detoxification).
• They are biosynthesized to aid the producers'
survival.
• Thus they are energy producer and
physiologically active.
• Secondary metabolites are divided into several
classes of various organic compounds.
 I- Carbohydrates and related
compounds
Compounds composed of carbon, hydrogen and oxygen as
polyhydroxy aldehydes or ketone alcohols: sucrose,
lactose, starch, gums, mucilage and pectin.
1- Gums:
• They are translucent, amorphous substances that are
frequently produced in higher plants as a protective after
injury.
• Gums are heterogeneous in composition. Upon
hydrolysis arabinose, galactose, glucose, mannose and
various uronic acids are produced.
• The uronic acids may form salts with calcium,
magnesium and other cations. Examples of gums are
gum Acacia and gum Tragacanth.
2- Mucilages :
1- They are polysaccharide complexes formed
from sugar and uronic acid units.
2- They are insoluble in alcohol but forming a
viscous non-adhesive colloidal solution with
water.
3- They are stained red with Ruthenium Red
reagent (pectose type present in Senna, buchu),
and with solution of Corallin soda (callose type
found in Squill). Others are stained by methylene
blue (neutral type of Fenugreek).
3- Pectin:
• It is formed of partially methoxylated
polygalactouronic acids.
• Pectin is a coarse or fine powder, yellowish
white in colour, almost odourless and has a
mucilaginous taste.
• Soluble in 20 parts of water and the solution is
viscous, colloidal and acidic to litmus.
• One part of pectin heated in nine parts of water
forms a stiff gel.
• Pectin is used as a suspending agent and is an
ingredient in many antidiarrheal formulations.
 II- Glycosides

Definition:
Glycosides are non-reducing organic compounds
that yield on hydrolysis with acids, alkalis or
enzymes:
1- A sugar (or glycone, formed of one or more
sugar units).
2- A non-sugar moiety (also called aglycone or
genin).
Glycosides are widely distributed in nature. They
usually accompanied with enzymes used in
either their synthesis or hydrolysis.
• Glycosides are considered as acetals or sugar ethers.

• Glycosides are generally soluble in water and hydroalcoholic

solvents due to the hydrophilic nature of the sugar.

• The higher the sugar content the less soluble in organic

solvent. The aglycones are soluble in organic solvents.
 Classification of glycosides
A- Phenolic glycosides:

They produce phenolic

aglycone when
subjected to
hydrolytic processes.
The phenolic
aglycone may be:
1- Simple phenolic
glycosides: e.g.
Arbutin present in Uva
ursi leaf
2- Flavonoid glycosides:
• They occur in plant in
both free aglycone
and /or as glycosides.

• This group is regarded

as C6-C3-C6
compounds in which
each C6 moiety is a
benzene ring e.g.
Diosmin glycoside of
Buchu and hespiridin
glycoside of Citrus
species.

• Chemical test:
flavonoides + KOH →
canary yellow colour
3- Anthraquinone
glycosides:
They are
pharmacologically
active constituents
of several laxatives
and purgatives of
plant origin e.g.
Senna, Aloe,
Cascara, Frangula,
Rhubarb.
1- Borntrager's test for anthraquinone glycosides:
Boil the powder with dil. HCl, filter, cool, shake with
organic solvent, separate organic layer, shake
with NH4OH, the aqueous layer becomes rose
pink or cherry red.

2- Modified Borntrager's test: in case of dianthrone

e.g. sennosoides:
a- Boil the powder with alc. KOH, filter.
b- Add dil. HCl to the filtrate and extract with ether.
c- Oxidize with H2O2.
d- Add NH4OH to the ethereal extract and shake,
a rose red colour is produced in the aqueous
layer.
4- Anthocyanin glycosides:
they are structurally related to flavonoids and
coloured.

They constitute the pigments of the coloured

petals of the flowers.

Their colours are affected by the pH of the

cell sap and ranges from red in acidic
medium to blue in alkaline medium. e.g.
Red Rose petals, karkadeh and corn silk.
 B- Cyanophore glycosides
(Cyanogenic)
• They yield HCN as one of the products of
hydrolysis.
• Examples are; amygdalin in bitter almond,
prunasin in wild cherry and linamarin in
linseed.
• Chemical test: by Guignard test: turns the
yellow colour of sodium picrate paper into
orange.
 C- Thioglycosides
(thiocyanate or sulphated glycosides)
• S-glycosides, S atom is
present conjugated to
glucose and a second S
atom present in a
sulfonated oxime
grouping.

• Singrin from black

mustard seeds giving allyl
isothiocyanate (mustard
irritant gas) upon
hydrolysis.
 D- Steroidal cardioactive
glycosides
• These drugs are used in
medicine as mainly to
increase the tone and
contractility of the cardiac
muscle.

• Also as diuretic due to the

increased renal
circulation.

• Thet are present in

leaves of Digitalis, seeds
of Strophanthus and the
bulb of Squill.
Structure activity relationship (SAR)
 Steroidal nucleus with alcoholic OH group at C3 at which sugar
is attached.

 Attachment of unsaturated lactone ring at C17. the lactone ring

is present either as a 5- membered ring (Cardinolides) e.g.
lannatosides in Digitalis or as 6- membered ring (bufadienolides)
e.g. Scillarin in Squill.

 Deoxy sugar, e.g. digitoxose.

 Detection of cardiac glycosides
Several chemical tests could be used for
identification of cardiac glycosides
Colour reactions due to aglycone moiety:
A- Reactions due to (-CH2-) group of the lactone
ring:
These are characteristic for the 5-mambered
lactone ring of cardenolides:
1- Kedde's test: card. + Kedde's reagent (3,5-
dinitrobenzoic acid + NaOH → violet colour.
2- Baljet's test: card. +Baljet's reagent (picric acid
+NaOH) → orange or red.
B- Reactions due to the steroidal nucleus:
Liebermann's test: card. in glacial acetic acid
+ H2SO4 → red, violet, blue to green.

Reactions due to the presence of 2-deoxy

sugar unit in the sugar moiety:
Keller-Killiani's test: card. in glacial acetic
acid containing traces of FeCl3, conc.
H2SO4 on the wall of the test tube → blue
ring is formed in between the two layers.
 E- Saponins
e.g. saponins of Quillaia bark

This group of glycosides is characterized by the following:

1. it foams in aqueous solution forming froth.

2. It causes haemolysis of red blood cells.

3. Drugs containing saponins are usually sternutatory and irritating

the mucous membrane of the eyes and the nose.

4. They are highly toxic when injected into blood stream.

5. They are used in cleaning industrial equipments and fabrics, also

as a powerful emulsifier of certain resins, fats and fixed oils.
 III- Tannins
• They are non-crystalline compounds that with
water form colloidal solutions possessing an acid
reaction and a sharp astringent taste.

• They precipitate gelatin and alkaloids.

• They precipitate protein and can combine with

protein of animal hide (Gold beater's test),
rendering them resistant to proteolytic enzymes
and so prevent their putrefaction.
• Uses of drugs containing tannins:
– Astringent in GIT and skin (haemostatic).
– In treatment of burns.
– Tanning of leather.
– Antidote of alkaloidal and heavy metals poisoning.
– Preparation of paints and ink.

Types of true tannins:

• True tannins: have molecular weight 1000-5000. there
are two main types of true tannins.

• Pseudotannins:
compounds of lower molecular weight than true tannins,
they don't respond to the gold beater's skin test.
 Hydrolysable Condensed
(Pyrogallol) (Catechol)
Hydrolysis Hydrolysable Non-Hydrolysable

Dry distillation Gives pyrogallol Gives catechol

FeCl3 Blue-black colour Green colour

Br2 water No ppt. Ppt

Examples Gall, Clove, Cinnamon, Tea,

Rhubarb Henna.
 IV- Alkaloids
Alkaloids, which mean alkali-like, are basic
nitrogenous compounds of biological origin, they
are physiologically active.

They occur in the form of salts with organic acids,

or in combination with specific acids e.g. opium
alkaloids occur with meconic acid .

generally alkaloidal bases are insoluble in water

but soluble in organic solvents. While alkaloidal
salts are soluble in water sparingly soluble in
organic solvents.
• Their physiological actions vary widely being
Analgesic and Narcotic e.g. morphine and
codeine
Central stimulant e.g. caffeine and strychnine
Mydriatic e.g. atropine
Myotic e.g. pilocarpine
Antiasthmatic e.g. ephedrine
Antihypertensive e.g. reserpine
smooth muscle relaxant e.g. atropine and
papaverine
skeletal muscle relaxants e.g. d-tubocurarine.
 Detection of alkaloids
Alkaloidal precipitants:
Most alkaloids are precipitated from neutral or
acidic solution by a number of reagents which
contain certain heavy metals e.g. Mayer's
reagent (potassium mercuric iodide solution)
gives creamy white ppt. with most alkaloids
except caffeine.
Alkaloidal colour reagents:
• The most common Dragendorff's reagent gives
orange colour.
 V- Volatile oils
Volatile or essential oils are volatile in steam.

They are secreted in oil cells, in secretion canals or

cavities or in glandular hairs.

They are generally mixtures of hydrocarbons and

oxygenated compounds derived from these
hydrocarbons.

These oxygenated constituents mainly determine the

odour and taste of volatile oils.
Volatile oils are used for flavoring e.g. oil of
Lemon, in perfumery e.g. oil of Rose

as spices e.g. Pepper, Clove , Cardamom

and for their therapeutic action as antiseptic

e.g. Thyme, antispasmodic e.g. Melissa,
Menthe, and carminative e.g. Chamomile.
 VI- Resins, Gum-resins and
similar substances
Resins are more or less solid, amorphous substances of
complex chemical nature, on heating they soften and
finally melt. They are insoluble in water but dissolve in
alcohol, chloroform and ether.

Resins are associated with volatile oil, so called oleoresin.

With gum and called gum resin.
With oil and gum and called oleo-gum resin.
Resins give brown colour with iodine reagent.

VII- Others:
Enzymes, vitamins, hormones, antibiotics, natural
insecticides, etc.........