Introduction to

Phytoconstituents
 SYLLABUS

Brief introduction to Primary and secondary

metabolites in plants with structures.

Self Study: Any two examples of each class of

phytoconstituents and significance of
phytoconstituents for therapeutic application

Study of their biosynthetic pathways with structures

(Including shikimic acid pathway and acetate
hypothesis, polyketides and terpenoids)
 Primary Metabolite

A primary metabolite is a kind of metabolite that is

directly involved in normal growth, development, and
reproduction.

It usually performs a physiological function in the organism

(i.e. an intrinsic function).

A primary metabolite is typically present in many organism

or cell.

This primary metabolism consists of chemical reactions that

allow the plant to live.
 Primary Metabolite

Primary metabolism comprises the chemical processes that every plant

must carry out every day in order to survive and reproduce its line.
Photosynthesis
Glycolysis
Citric Acid Cycle (Krebs cycle)
Synthesis of amino acids
Transamination
Synthesis of proteins and enzymes
Synthesis of coenzymes
Synthesis of structural materials
Duplication of genetic material
Reproduction of cells (growth)
Absorption of nutrients
 Secondary Metabolite

A secondary metabolite is not directly involved in

those processes, but usually has an important
ecological function (i.e. a relational function).

A secondary metabolite is typically present in a

taxonomically restricted set of organisms or cells
(Plants, Fungi, Bacteria).
 Secondary Metabolite

Plant secondary metabolism produces products that aid in the

growth and development of plants but are not required for the plant to
survive.

Secondary metabolism facilitates the primary metabolism in plants.

In order for the plants to stay healthy, secondary metabolism plays a
pinnacle role in keeping all the of plants' systems working properly.

A common role of secondary metabolites in plants is defence

mechanisms. They are used to fight off herbivores, pests, and pathogens.

Secondary metabolites are used in anti-feeding activity, toxicity or acting

as precursors to physical defence systems.
 Primary versus Secondary Plant Metabolism

 Primary metabolism in a plant  secondary metabolites are not essential to

comprises all metabolic pathways that the functioning of the plant
are essential to the plant's survival.
 Secondary plant metabolites are used in
 Primary metabolites are compounds signalling and regulation of primary
that are directly involved in the growth metabolic pathways.
and development of a plant
 Plant hormones, which are secondary
metabolites, are often used to regulate the
 E.g. Sugar, Amino acids, fatty acids
metabolic activity within cells and oversee
the overall development of the plant.

 secondary plant metabolites help the

plant maintain an intricate balance with
the environment, often adapting to match
the environmental needs.
 E.g. colouring of a plant can attract
pollinators and also defend against attack
by animals.
Biosynthesis of Primary Metabolites (Carbohydrates)

Carbohydrates are the first products formed in

photosynthesis, and are the products from which
plants then synthesize their own food reserves as
well as other chemical constituents.

These materials then become the foodstuffs of other

organisms.

Secondary metabolites are ultimately derived from

carbohydrate metabolism.
 PHOTOSYNTHESIS

Photosynthesis is the process by which autotrophic

organisms use light energy to make sugar and
oxygen gas from carbon dioxide and water

Almost all plants are photosynthetic autotrophs, as

some bacteria and protists
 Glycolysis: Embden-Myerhof Pathway

Oxidation of glucose

Products:
–2 Pyruvate
–2 ATP
–2 NADH
Functions
Provide ATP energy
Generate intermediates for other pathways (the most
important is pyruvate).
 The most important building blocks employed in the
biosynthesis of secondary metabolites are derived
from:

1. Acetyl coenzyme A (acetyl-CoA)

2. Shikimic acid
3. Mevalonic acid
4. 1-deoxyxylulose 5-phosphate
5. Amino acids
 Alkaloids

Coumarins Terpenoids

Tannins Steroids
Secondary
Metabolites

Flavanoids Saponins

Natural
Glycosides
Phenols
 SECONDARY METABOLITES

Secondary metabolites can be classified on the basis of chemical

structure (for example, having rings, containing a sugar),
composition (containing nitrogen or not), their solubility in various
solvents, or the pathway by which they are synthesized (e.g.,
phenylpropanoid, which produces tannins).

A simple classification includes three main groups:

1. terpenes (made from mevalonic acid, composed almost entirely of
carbon and hydrogen),
2. phenolics (made from simple sugars, containing benzene rings,
hydrogen, and oxygen), and
3. nitrogen-containing compounds (extremely diverse, may also
contain sulfur).
 Alkaloids

Alkaloids are a group of naturally occurring

chemical compounds (natural products) that contain
mostly basic nitrogen atoms.

they are basic.

they contain one or more nitrogen atoms (usually in
a heterocyclic ring) and
they usually have a marked physiological action on
man or other animals
 Deviation from Definition:

 Basicity: Some alkaloids are not basic e.g.

Colchicine, Piperine, Quaternary alkaloids.

 Nitrogen: The nitrogen in some alkaloids is

not in a heterocyclic ring e.g. Ephedrine,
Colchicine, Mescaline.

 Plant Origin: Some alkaloids are derived

from Bacteria, Fungi, Insects, Frogs,
Animals.
 Classification:

 True (Typical) alkaloids that are derived from amino

acids and have nitrogen in a heterocyclic ring. e.g
Atropine

 Protoalkaloids that are derived from amino acids and do

not have nitrogen in a heterocyclic ring. e.g Ephedrine

 Pseudo alkaloids that are not derived from amino acids

but have nitrogen in a heterocyclic ring. e.g Caffeine

 False alkaloids are non alkaloids give false positive

reaction with alkaloidal reagents.
 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

 Function in Plants

 They may act as protective against insects and herbivores

due to their bitterness and toxicity.

 They are, in certain cases, the final products of

detoxification (waste products).

 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.
 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.
 The salts of sanguinarine are copper-red.
 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.
 Physical Properties:

IV- Isomerization:
Optically active isomers may show different physiological
activities.
l-ephedrine is 3.5 times more active than d-ephedrine.
l-ergotamine is 3-4 times more active than d-ergotamine.
d- Tubocurarine is more active than the corresponding l-
form.
Quinine (l-form) is antimalarial and its d- isomer quinidine
is antiarrythmic.
The racemic (optically inactive) dl-atropine is
physiologically active.
 Chemical Properties:

I- Nitrogen:
Primary amines R-NH2 e.g. Norephedrine
Secondary amines R2-NH e.g. Ephedrine
Tertiary amines R3-N e.g. Atropine
Quaternary ammonium salts R4-N e.g d-Tubocurarine

II- Basicity:
R2-NH > R-NH2 > R3-N
Saturated hexacyclic amines is more basic than aromatic
amines.
 According to basicity Alkaloids are classified
into:

Weak bases e.g. Caffeine

Strong bases e.g. Atropine
Amphoteric * Phenolic
Alkaloids e.g. Morphine *Alkaloids with
Carboxylic groups e.g. Narceine
Neutral alkaloids e.g. Colchicine
 Qualitative test for Alkaloids:

 Precipitation Reagents:
They are used to:
1- Indicate the absence or presence of Alkaloids
2- Test for complete of extraction

Disadvantages: Some non alkaloids interfere such

as Proteins, lactones, coumarins
 Classification of Alkaloidal precipitating agents:

1- Reagents that form double salts:

a- Mayer’s Reagent: Potassium Mercuric Iodide.
b- Dragendorff’s Reagents: Potassium Iodobismethate.
c- Gold Chloride.

2- Reagents Containing Halogens:

a- Wagner’s Reagent: Iodine/ Potassium Iodide.

3-Organic Acids:
a- Hager’s Reagent: Picric Acid
b- Tannic Acid.

4- Oxygenated High Molecular Weight Acids:

a- Phosphomolybdic acid
b- Phosphotungestic acid
c- Silicotungestic Acid
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.
 Plant material and solvent

Organic solvent dissove Alkaloids

Organic solvent dissove Impurities
Extract

Concentration Acidification

Alkalinization

Acidified Extract (Alk. as salts)

Alkaline aqueous layer
 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

There are two broad divisions:

I. Nonheterocyclic or atypical alkaloids sometimes

called protoalkaloids or biological amines.

II. Heterocyclic or typical alkaloids divided into 14

groups according to their ring structure.
 l. Nonheterocyclic alkoloids

 Hordenine or N-methyltyramine

 Mescaline related to tryptamine

 Ephedrine

 Colchicine (tropolone nucleus with nitrogen in side-chain)

 Erythromycin (antibiotic)

 Jurubin (steroid with 3 -amino group)

 Pachysandrin A (steroid with N –containing C- 17 sidechain)

 Toxol modified diterpene pseudo alkoloid

 ll. Heterocyclic olkoloids

1. Pyrrole ond pyrrolidine

Hygrines, Stachydrine

2. Pyrrolizidine
Symphitine, echimidine, Senecionine, seneciphylline etc .

3. Pyridine and piperidine

Trigonelline, Coniine, Arecoline, Lobeline, Pelletierine,
Nicotine( pyridine+ pyrrolidine), Anabosine, Piperine, Ricinine

4. Tropone( piperidine,/N-methyl-pyrrolidine)
Hyoscyomine, atropine, hyoscine, meteloidine etc
5)Quinoline
Quinine, quinidine , cinchonine, cinchonidine, cusporin

6. lsoquinoline
Papaverine, narceine, narcotine, Corydaline, Hydrastine, berberine, Emetine, cephaeline,
Tubocurorine, Morphine, codeine, Erythroline, Galanthamine

7. Aporphine (reduced isoquinoline/naphtholene)

Boldine

8. Norlupinane
Sparteine, cytisine, luponine, laburnine

9. lndole or benzopyrrole
Ergometrine, ergotamine, Lysergic acid amide, clavine alkoloids, Physostymigine, Ajmaline,
serpentine, reserpine, Yohimbine, aspidospermine, Vincristine, Vinblastine
10. Indozolidine
Castanospermine

11. Imidazole or glyoxaline

Pilocarpine

12. Purine
Caffeine

13. Steroidal
Salanidine

14. Terpenoid
Aconitine, atisine
Phenylalkylamines:
CH2 CH CH3
e.g. Ephedrine
NH2

Pyridine and piperidine

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

Isoquinoline N
e.g. papaverine

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

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

Terpenoid
e.g. Taxol
TERPENES
 Terpenes are unsaturated compounds formed by joining
together isoprene units.

 Terpenes containing oxygen or other functional groups are

known as ‘terpenoids’.

 During the 19th century, chemical works on turpentine led to

name "terpene" the hydrocarbons with the general formula
C10H16 found in that complex plant product.

 These terpenes are frequently found in plant essential oils.

 Terpenoids are
extraordinarily diverse but
they all originate through
the condensation of the
universal phosphorylated
derivative of hemiterpene,
isopentenyl diphosphate
(IPP) and dimethylallyl
diphosphate (DMAPP)
giving geranyl
pyrophosphate (GPP).
 Isoprene

Isoprene is the common name for

2-methylbuta-1,3-diene

CH3 H3C CH2

H2C C CH CH2 C CH

H2C
 Isoprene

Head Tail

CH3 CH2

C CH =

CH2

Isoprene
(2-methylbuta-1,3-diene)

One isoprene unit contains five carbon atoms

 Building terpenes from isoprene

Isoprene units can be linked:

head to tail to form linear terpenes

in rings to form cyclic terpenes.

 Structure and classification

 Terpenes are hydrocarbons resulting from the combination of

several isoprene units. modified terpenes according to the
number of isoprene units used:
 Hemiterpenoids, 1 isoprene unit (5 carbons)
 Monoterpenoids, 2 isoprene units (10C)
 Sesquiterpenoids, 3 isoprene units (15C)
 Diterpenoids, 4 isoprene units (20C)
 Sesterterpenoids, 5 isoprene units (25C)
 Triterpenoids, 6 isoprene units (30C)
 Tetraterpenoids, 8 isoprene units (40C)
 Polyterpenoid with a larger number of isoprene units
Terpenoids can also be classified according to the
number of cyclic structures they contain.
 ACYCLIC MONOTERPENES

They can be considered as derivatives of 2,6-

dimethyloctane.
 Myrcene – a linear terpene

Head Tail Head Tail

H3C CH2

C CH

H2C

• Myrcene is a component of plants, including bay,

ylang-ylang and thyme.
 MONOCYCLIC MONOTERPENES

They are derived from cyclohexane with an isopropyl

substituent.

Limonene is an important volatile emitted by the holm oak,

and acts as allelochemical in inhibiting seed germination of other
plant species.
 BICYCLIC MONOTERPENES

H3C CH3
CH

C
H2C CH2

HC C
CH O

CH3

Thujone
(Absinthe)
 BICYCLIC MONOTERPENES
 Thujone is best known
for being a toxic chemical
in absinthe, a product
extract from Artemisia
absinthium.

 Pharmacologically,
thujone acts mainly on
the GABA receptors in
the brain and exhibits
psychoactive
response.
 SESQUITERPENES
 Sesquiterpenoids are defined as the group of 15 carbon
compounds derived by the assembly of 3 isoprenoid units and
they are found mainly in higher plants but also in invertebrates.

 Sesquiterpenes, with monoterpenes, are an important constituent of

essential oils in plants.

 They are the most diverse group of isoprenoids.

 In plants, they function as pheromones and juvenile hormones.

 Sesquiterpene structures present several acyclic, mono-, bi-, tri-,

and tetracyclic systems.
 Acyclic compounds

The acyclic
representative are also
called farnesans, term
derived from the basic
structure, farnesol.

Farnesol and nerolidol
are very common and
are isolated from
essential oils of various
sources. 
 Cyclic compounds

 Abscisic acid plays a
key role in plants in the
regulation of
stomatal closure by
regulating ion
channel activities and
water exchanges
across the plasma
membrane of guard
cells. 
Some important sesquiterpenes
 Bicyclic sesquiterpenes
with a driman unit are
widespread in plants,
liveworts, fungi and certain
marine organisms
(sponges).

Driman squeleton
Capsidiol is a
sesquiterpenoid
compound that
accumulates in
tobacco Nicotiana
tabacum and chili
pepper Capsicum
annuum in response to
fungal infection.

It is considered as a
phytoalexin. Capsidiol
 DITERPENES
 They have 20 carbon atoms and are derived
from geranylgeraniol pyrophosphate.
 The diterpenes have
exceptionally open
chain
 Phorbol is a diterpene
isolated in 1934 from
croton oil (seeds
of Croton tiglium). 

Phorbol
R : myristic acid (C14:0),
Ac : acetate group
 SESTERPENES
They are derived from geranylfarnesol pyrophosphate
and have 25 carbon atoms.
Three examples of sesterpenes are shown below.
 TRITERPENOIDS

They form a large group of natural substances which

includes steroids and consequently sterols.
Squalene is the immediate biological precursor of all
triterpenoids. 
Among the large number of triterpenoid
structures,  some of them are shown below.
 Steroids are modified triterpenes which derived also
from squalene by cyclization, unsaturation and
substitution.
 The nucleus of all steroids is the tetracyclic C17
hydrocarbon 1,2-cyclopentanoperhydrophenanthrene
(gonane or sterane) substituted by methyl groups at
C10 and C13, as well as an alkyl side-chain at C17.
 Steroids may possess a nucleus derived from the
former one by one or more C-C bond scissions or ring
expansions or contractions.
Unsaturated steroids with most of the skeleton of
cholestane containing a 3b-hydroxyl group and an
aliphatic side chain of 8 or more carbon atoms
attached to position 17 form the group of sterols.
 Other pentacyclic
triterpenoids based on
the lupane skeleton
include a very large
number of naturally
occurring members
with different
functional groups which
are found in vegetables
and fruit.
 Among them, lupeol is
one of the most
ubiquitous compounds. 
GLYCOSIDES
 Definition:

 Organic natural compounds present in a lot of plants and

some animals, these compounds upon enzyme or acid
hydrolysis give one or more sugar moiety (glycone) and non
sugar moiety (aglycone) or called genin.
 Classification:

Atom from the aglycone involved in the glycosidic linkage:

 Aglycone- O- Sugar O-glycosides
 Aglycone- C- Sugar C-glycosides
 Aglycone- S- Sugar S-glycosides
 Aglycone- N- Sugar N-glycosides
Number of sugars:
 One sugar monosides e.g. Salicin.
 Two sugarBiosides e.g. Diosmin.
 Three sugars Triosides e.g. Digoxin.

Nature of the glycoside:

 Primary glycosides: Originally present in the plant e.g. Purpurea A
 Secondary glycosides: Resulted from removal of one sugar from the
primary glycosides e.g. Digitoxin
Type of the glycosidic linkage:
 a- glycosides
 b- glycosides
Botanical source:
 Digitalis glycosides
 Senna glycosides.
Therapeutic use:
 Analgesic glycosides.
 Purgative glycosides.
 Cardiac glycosides.
Chemical nature of the aglycone:
 Flavone glycosides.
 Steroidal glycosides.
 Aldehydic glycosides.
 Classification

(a) Cardioactive glycosides: Digitalis, Strophanthus and

white squill
(b) Anthraquinone glycosides: Cascara, Aloe, Rhubarb,
Cochineal and Senna
(c) Saponin glycosides: Glycyrrhiza, Sarsaparilla
(d) Cyanophore glycosides: Wild cherry
(e) Isothiocyanate glycosides: Black Mustard
(f) Lactone glycosides: Cantharide
(g) Aldehyde glycosides: Vanilla
(h) Miscellaneous glycosides: Gentian, Quassia, Dioscorea
 Physical Characters:

Solids either amorphous or crystalline.

Non volatile.
Usually bitter in taste.
Soluble in water and polar organic solvents.
Reduce Fehling’s solutions only after hydrolysis.
 Stability of Glycosides:

1- Effect of acid hydrolysis:

Acids split sugars from the aglycones.
The acetal linkage is more readily cleaved than
the linkage between the individual sugars of the
sugar chain.
C-glycosides are resistant to acid hydrolysis.
2- Effect of alkaline hydrolysis:
A- Strong alkalis:
Hydrolysis of ester groups.
Opening of lactone rings e.g. Cardiac glycosides.

B- Mild alkalis:
Hydrolysis of ester groups e.g. Lanatoside A to
Purpurea A
Opening of lactone rings e.g. Cardiac glycosides.
3- Enzymatic hydrolysis:

 Split the sugars stepwise starting from the

terminal sugars.
 All plants producing glycosides have enzyme that
can hydrolyze these glycosides.
 Enzymes are specific for the type of glycosidic
linkages:
 Emulsin can hydrolyze b- glycosides
 Invertase can hydrolyze a- glycosides
 Myrosin can hydrolyze s-glycosides.
 Extraction and Isolation
 Because of the wide range of physical and chemical properties
of glycosides and other constituents associated with them, no
common general method for their isolation is recommended.
 Water, methanol, water-ethanol and ethanol are the most
common solvents for extraction of glycosides.

Precautions before extraction

 Deactivation of enzymes:
 Drying for 15-30 min at 100 oC followed by slow drying at a low
temperature.
 Dipping the fresh material into boiling water or boiling alcohol for
10-20 min.
 Boiling the fresh plant material with acetone.
 Carrying out the extraction at very low temp.
 Freeze-drying of the plant material before extraction (lyophilization).
 Carrying the extraction in the presence of (NH ) SO .
4 2 4
  Maintenance of neutral conditions:
 Neutral pH should be assured before and during
extraction because:
 Acidity may result in hydrolysis. This is overcome by
addition of CaCO3.
 Mild alkalinity may sometimes produce racemization.

 Defatting of fat-rich organs (e.g. seeds) before

extraction:
 High amounts of lipids hinder glycoside extraction.
Defatting is usually carried with petroleum ether
 Alcoholic and Phenolic Glycosides

1- Salicin
 Source: Salix species (Willow bark).
 Nature: Primary achholic and Phenolic
glycoside (monoside).
 Uses: Analgesic- Antipyretic- Anti-
inflammatory.

CH2OH CH2OH
CH2OH
Acid Enzyme OH
O
Saligenin
Saliretin (Salicyl alch.)
HOH2C
O-glc
+ +
Glucose Glucose
 2- Arbutin & Methyl Arbutin
 Source: Uva Ursi (Bearberry leaves).
 Nature: Primary Phenolic glycoside
(monoside).
 Uses: Diuretic- Bactericidal.
OCH3 OH
OH

Hydrolysis
+ Glucose
OH
Hydroquinone
O-glc O-glc
Methylarbutin Arbutin
 Aldehydic Glycosides

1- Glucovanillin
 Source: Vanilla pods.
 Uses: Flavouring agent- Spray reagent.

Glucovanillin Vanillin
CHO CHO
Enzymatic Hydrolysis
+ Glucose

OCH3 OCH3
O-glc OH
Green vanilla pods Brown vanilla pods
Bitter in taste Sweet in taste
Odourless Vanilla odour
 Commercial Preparation of Vanillin
CH 2-CH=CH 2 CH=CH-CH 3
Iso-eugenol
Eugenol
Vanillin
KOH Oxidation
OCH 3 OCH 3
OH OH

Guaiacol CHCl3+ NaOH

Vanillin
OCH 3 Reflux
OH

CH=CH-CH 2OH

H2SO4/K2Cr2O7
Coniferin Vanillin
OCH 3
O-glc
 Cyanogenic Glycosides

 Cyanogenic glycosides (Cyanogentic or

Cyanophore Glycosides) are O-glycosides yielding
HCN gas on hydrolysis .
 They are condensation products of HCN to a
carbonyl compounds (Cyanohydrin).
 1- Amygdalin
 Source: Bitter Almond.
 Structures: It is a Bioside of mandilonitril.

O H

HCN + CHO CH

CN

Mandilonitril

1-6 linkage
O glc glc O glc

CH CH
Amygdalase Prunase
CN CN
Amygdalin Prunasin
 2- Linamarin
 Source: Linseed.
 Structures: It is the glycosidic derivative of the cyanohydrin of
acetone.
H3C O glc
C
H3C CN
 Uses:
 Linamarin has a molluscecidal activity.(pesticide against
mollusc)
 Amygdalin is used for the preparation of Benzaldehyde.

 Cyanogenic glycosides have role in cancer treatment.

Test for Cyanogenic Glycosides:

 Reduce plant material to small pieces and moisten with

water.
 Incubate at temp. less than 45 0C for 30 60 mins with the
neck of the flask stoppered and have suspended sodium
picrate paper.
 The paper will turns brick red due to the release of HCN
gas.
 Thioglycoside
Glucosinolates- Sulphur Glycosides

 They are S-glycosides widely distributed in family

Cruciferae.
Sinigrin: In seeds of Brassica nigra (black mustard).
Sinalbin: In Seeds of Brassica alba (white mustard).
S-Glc
H C
H2C C C
H2 N-O-SO3K

Sinigrin
Uses: Rubefacients, Counter irritants and condiment.
 Garlic

 It consists of the bulb of Allium sativum Fam. Liliaceae.

 The intact cells of garlic contain an odorless, sulfur-containing
amino acid derivative (+)-S-allyl-L-cysteine sulfoxide, commonly
known as alliin.
 Alliin is hydrolyzed by the effect of alliinase enzyme present in
different cells after crushing into allicin (diallyl thiosulfinate).
 Allicin is responsible for the characteristic odor and flavor of garlic.
 Allicin is a potent antibacterial, antihyperlipidemic, and it inhibits
platelet aggregation and enhances the blood fibrinolytic activity.

O O

S COOH
Alliinase S
H S + H2O
NH2
Alliin Allicin
TANNINS
 7. Tannins
Historically, the importance of tannin-containing
drugs is linked to their tanning properties, in other
words their ability to transform fresh hides into an
imputrescible material: leather.

Tannins are "phenolic natural products that

precipitate proteins from their aqueous solutions".
The consequence of tanning is the formation of bonds
between the collagen fibers in the hide, which imparts
resistance to water, heat, and abrasion. This capability of
tannins to combine with macromolecules explains why
they precipitate cellulose, pectins, and proteins; it also
explains their characteristic astringency and tartness: by
precipitating the glycoproteins contained in saliva,
tannins make the latter lose its lubricating power.

Most true tannins have molecular weights from about

1000  5000.
 Pseudotannins

They are compounds of lower molecular weight than

true tannins and they do not respond to the
goldbeater's skin test.

Examples of drugs containing Pseudotannins are:

• Gallic acid: Rhubarb
• Catechins: Guarana, Cocoa
• Chlorogenic acid: Mate, Coffee
• Ipecacuanhic acid: ipecacuanha
Function of tannins in plants

1. Tannins are considered the source of energy through

their oxygen content.
2. They serve as a protective to the plant (plant
antiseptics).
3. They may have function in respiratory activity, i.e.
in the mechanisms of hydrogen transfer in plant
cells.
4. Tannins play an important part in the acceptance of
many foods and beverages by consumers e.g. tea,
cocoa.
Classification of tannins

In higher plants, two groups of tannins are generally

distinguished, which differ by their structure, as well
as their biosynthetic origin: hydrolysable tannins and
condensed tannins.

Hydrolysable tannins
Hydrolysable tannins are esters of a sugar (or related
polyol) and of a variable number of phenolic acid
molecules.
The sugar is most generally glucose.
The phenolic acid is either gallic acid, in the case of
gallitannins, or Ellagic acid, in the case of the tannins
conventionally referred to as ellagitannins.

Ellagic acid can arise by lactonization of

hexahydroxydiphenic acid (= HHDP) during chemical
hydrolysis of the tannin.

Hydrolysable tannins were formerly known as

pyrogallol tannins, because on dry distillation gallic
acid and similar components are converted into pyrogallol.
Biosynthetically, gallic acid (= 3,4,5-
trihydroxybenzoic acid) arises from the metabolism of
shikimic acid.

Examples of drugs containing Hydrolysable tannins:

Gallitannins: rhubarb, cloves, Chinese galls, Turkish
galls, hamamelis, chestnut and maple. Ellagitannins:
pomegranate rind, pomegranate bark, eucalyptus
leaves, and oak bark.
Condensed tannins (proanthocyanidins)

Condensed tannins or proanthocyanidins are

polymeric flavans. They consist of flavan-3-ol units
linked together by carbon-carbon bonds, most often
48 or 46, which result from coupling between the
electrophilic C4 of a flavanyl unit from a flavan-4-ol
or flavan-3,4-diol and a nucleophilic position (C-8, less
commonly C-6) of another unit, generally a flavan-3-ol.

 Unlike hydrolysable tannins, these are not readily

hydrolyzed to simpler molecules and they do not
contain a sugar moiety.
Biosynthetically, flavonoids are derived from
acetate and shikimate pathways.
Condensed tannins occur due to polymerization
(condensation) reactions between flavonoids.
The polymers may include up to 50 monomer units.
On treatment with acids or enzymes condensed
tannins are converted into red insoluble compounds
known as phlobaphenes. Phlobaphenes give the
characteristic red colour to many drugs such as red
cinnamon bark.
Examples of drugs containing Condensed tannins:
Some drugs (e.g. tea, hamamelis leaves and hamamelis
bark) contain both hydrolysable and condensed tannins. The
following are rich in condensed tannins.
(1) Barks: cinnamon, wild cherry, cinchona, willow, acacia, oak
and hamamelis
(2) Roots and rhizomes: krameria (rhatany) and male fern
(3) Flowers: lime and hawthorn
(4) Seeds: cocoa, guarana, and kola
(5) Leaves: hamamelis, hawthorn and tea, especially green tea
(6) Extracts and dried juices: catechu, acacia and mangrove
cutches
 Properties and tests of tannins

Tannins are soluble in water, dilute alkalis, alcohol, glycerol and

acetone, but generally only sparingly soluble in other organic
solvents.

Solutions precipitate heavy metals, alkaloids, glycosides and

gelatin.

With ferric salts, gallitannins and ellagitannins give blue-black

precipitates and condensed tannins brownish-green ones. If a very
dilute ferric chloride solution is gradually added to an aqueous
extract of hamamelis leaves (which contains both types of tannin),
a blue colour is produced which changes to olive-green as more
ferric chloride is added. Other useful tests are the following:
1. Goldbeater's skin test
Soak a small piece of goldbeater's skin in 2%
hydrochloric acid; rinse with distilled water and
place in the solution to be tested for 5 min. Wash
with distilled water and transfer to a 1% solution of
ferrous sulphate. A brown or black colour on the
skin denotes the presence of tannins. Goldbeater's
skin is a membrane prepared from the intestine of
the ox and behaves similarly to an untanned hide.
2. Gelatin test
Solutions of tannins (about 0.5-1 %) precipitate a 1%
solution of gelatin containing 10% sodium chloride.
Gallic acid and other pseudotannins also precipitate
gelatin if the solutions are sufficiently concentrated.
3. Phenazone test
4. Test for catechin
5. Test for chlorogenic acid
Medicinal and biological properties

The applications of tannin-containing drugs are

limited, and result from their affinity for proteins.
Tannin-containing drugs will precipitate protein and
have been used traditionally as styptics and internally
for the protection of inflamed surfaces of mouth and
throat.
They act as antidiarrhoeals and have been employed as
antidotes in poisoning by heavy metals, alkaloids and
glycosides.
sumac