Amal Kabbash, Professor of Pharmacognosy 1

Vice Dean for Education and Students Affairs

 ILOS of the Course:

Intended Learning Outcomes

a- Learning and Understanding

b- Intellectual Skills

c. Professional and Practical Skills

d- General and Transferable Skills

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Intended Learning Outcomes of Course:
ILOS
a- Learning and understanding
a1- Enumerate the several groups of alkaloids
and volatile oils.

a2- Describe the botanical occurrence,

extraction, isolation, identification and
determination procedures.

a3- Describe the biosynthesis and the therapeutic

effects of different alkaloids and volatile oils.

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b- Intellectual Skills

b1-Differntiate between the chemical

structures and uses of different groups of
alkaloids and volatile oils.

b2- Summarize the possible leads to new

drugs depending on natural product
templates

b3- Determine the different methods used

for quantitative and qualitative
determination of different groups of alkaloids
and volatile oils.
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c. Professional and Practical Skills

c1- Summarize the practical

phytochemical procedures.

c2- Provides examples of the different

groups of alkaloids and volatile oils in terms
of their uses, chemical group, origin.

c3- Identify different groups of alkaloids

and volatile oil

c4- Analyze different groups of alkaloids

and volatile oil 5
d- General and Transferrable Skills

d1- Perform search and retrieve of information

d2- Collaborate in laboratory work

d3- Collaborate in the writing of reports

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 Course Evaluation
• Total Marks: 500
• Mid term: 50
• Practical exam.: 100 (include attendance, note,
behavior, activity)
• Oral exam.: 100 (Lecture attendance may affect)
• Final written exam.: 250
(Problem based evaluation)????

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Essential oils, Volatile Oils, Etherial oils
Terpenoids
Definition
Difference from fixed oils
Distribution, localization and function
Uses
Physical characters
Methods of preparation
Quality control
Storage
Chemistry
Classification 12
 VOLATILE, ETHEREAL or ESSENTIAL OILS

 "Volatile" or "ethereal": as they easily evapor

ate on exposure to air at room temperature
 "Essential": contains the "essence of" the plant's
fragrance i.e: the characteristic fragrance of the
plant from which it is derived
 Defination: Class of volatile compounds that
give plants their characteristic odors and are
used especially in perfumes and flavorings, and for
aromatherapy
 Aromatic: since most have aromatic odor 13
 Major Differences between volatile & fixed oils
Property Volatile oil Fixed oil
Volatilization at Volatile Non-volatile
ordinary temperature

Solubility Soluble in organic Limited solubility in organic

solvents (ether, CHCl3) & solvents, almost insoluble in
alcohol alcohol

Stain on filter paper Transient Permanent & greasy

Composition Complex mixtures of Triglycerides ester of fatty

hydrocarbons & acids e.g. palmitic, stearic,
oxygenated compounds oleic……..

Response to long Resinification Rancidity

exposure to air & light
(oxidation)

Saponification with Negative Positive

caustic alkali (KOH)

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 Distribution, localization and function

 Distribution
• In higher plants, different families as: Rutaceae, Myrtaceae,
Lamiaceae (Labiatae), Lauraceae,…..
• Accumulate in all types of vegetable organs:
Flowers (rose), Leaves (eucalyptus), Barks (cinnamon),

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Woods (Sandalwood) Roots (vetiver.)

Rhizomes Fruits (star anise), Seeds (nutmeg)

(ginger),

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 Localization
Usually in specialized
histological structures
 Oil cells: Lauraceae,
Zingiberaceae
 Glandular trichomes:
Lamiaceae
 Secretory cavities:
Rutaceae, Myrtaceae
 Secretory canals:
Apiaceae (Umbelliferae).

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 Uses of Volatile Oils
1. Therapeutic & medicinal uses: local stimulants,
carminatives, diuretics, mild antiseptics, local
irritants, anthelmintics, parasiticides, respiratory
infection, immune enhancing, anti-inflammatory,
2. Spices & condiments: in food (to impart aroma &
flavor) or as preservatives

3. Flavoring agents: in food (e.g. beverages, soups,

bakery products, confectionery) &
pharmaceutical industries
4. Aromatic agents: in all types of perfume
industries (cosmetics, soaps, deodorizers)

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Function to the plants itself
• Attracting (for polination) or repelling
insects
• Protection from heat or cold
• As antibacterial agents

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 Physical properties
 Possess characteristic odors ( lemon and lavender oils )
 Liquids and volatile at ambient temp.
Except anise oil becomes solid at 15.5°C and rose oil solidify
at 18 °C
 Soluble in common organic solvents. Sparingly soluble in
water.
 Mostly lighter than water, except clove, winter green and
cinnamon oils are heavier ( aromatic oxygenated oils).
 Most of them rotate the Plan of polarized light.

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 Methods of preparation
there are four main methods

Distillation
• Water distillation
• Water and steam distillation
• Direct steam distillation
Scarification and expression
 Sponge method
 Ecuelle a piquer
 Expression of rasping

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Extraction with solvents
Volatile solvents
Non volatile solvents
 Enfleurage method
 Pneumatic method
 Maceration method
 Supercritical fluid extraction
Enzymatic hydrolysis
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 Methods of Preparation of Volatile Oils

Distillation Scarification & Expression Extraction Enzymatic SFE

Hydrolysis
Water Distillation Sponge Method Extraction with Volatile
Solvents
Steam Distillation Ecuelle a piquer
Method Extraction with Non-Volatile
Solvents
Water & Steam Expression of Rasping Process
Distillation Enfleurage Method
Pneumatic Method
Direct Steam
Maceration Method
Distillation

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Selection of the suitable method is done
according to :

1. The condition of the plant material (moisture content,

degree of comminution)

2. The localization of the oil in the plant (superficial or

deep)

3. The amount of the oil

4. The nature of the oil constituents

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 Distillation methods

Application: preparation of thermostable oils,

present in large amounts & not rich in
esters (e.g. oils of turpentine, peppermint, ..

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 Distillation
Converts the essential oils into vapor and then
condenses the vapor back into a liquid.
Oil of terpentine Boils at 160 oC, water
100 oC
Oil of terpentine + water 95.5 oC
• Advantage:Wide Application
• Disadvantage

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 Water distillation
• Plant material (dried) is completely immersed in wat
er and the still is brought to the boil, when the cond
ensed material cools down water + v. oil
• e.g oil of turpentine.

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 Direct steam distillation
• Plant material (fresh) is placed in a still and
steam is forced through the material. The hot
steam helps to release the aromatic molecule
s from the plant material and carries them (oil
droplets) to the condensation chamber.
• e.g oil of peppermint

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• The receiver (Florentine flask), allows the oil to col
lect as a separate upper layer (oils lighter than wat
er) or lower layer (oils heavier than water), while
the aqueous layer saturated with oil (Aromatic wate
r) is siphoned off.
• When it is automatically returned to the steam bo
iler for the generation of more steam and to reco
ver the dissolved oil, this is called "Cohobation".

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• Water and steam distillation
Plant material (fresh or dried) is immersed
in water in a still, which has a heat source and
steam is fed into the mixture (water + crushed
plant).

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Steam distillation of lavender. King’s Lynn, Norfolk, UK

1 pint(=0.75 ml) essential oils are obtained from ¼ ton (=225 kg)
of dried lavenders by steam distillation 35
 Scarification & Expression Methods
Principle
Mechanical procedures carried at room
temperature & based on puncturing & s
queezing of the plant material to liberat
e the oil, which is collected.

Applications
Preparation of heat sensitive oils, present in large
amounts in outer peels of fruits e.g. Citrus fruits (Rutaceae)36
as orange, lemon & bergamot.
 Scarification and expression
These are cold methods of extraction, mostl
y used in the extraction of citrus essential oil
s.
• Sponge method

Citrus fruits are cut into halves, the juice was r

emoved and the pericarp soaked in water, th
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en squeezed against a sponge. The sponge i
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 Scarification and expression
Ecuelle a piquer
The fruits are placed in a
device and rotate with
puncturing the oil glands
in the peel of the fruits.
Expression of rasping
The outer region of pericarp c
ontaining oil glands is remov
ed by a grater. The rasping i
s strongly 39

pressed in horse-hair
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 Extraction with solvents
For oils:
Decompose by the action of steam.
Present in extremely small quantities
E.g. oil of Jasmine, violet, Tuberos
e………
Extraction using volatile solvents
Volatile solvents as pet. ether,
hexane,.. are used by
percolation or continuous
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extraction (Soxhlet)
Soxhlet

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Non volatile solvent extraction methods-Ap
plication
Preparation of delicate flower oils
e.g. jasmine, violet and tuberose
which are:

1. Present in very small

amounts, not easily obtained
by distillation or expression

2. Oils formed of thermolabile

constituents (i.e. easily
decomposed by heat)
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Extraction using non volatile solvent
s
Enfleurage method
Wooden frames, each enclosing a sheet
of glass. Glass plates are covered with
a layer of fat. The petals are spread acr
oss and pressed in.
The saturated fat is then scraped and extr
acted with alcohol.

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Enfleurage method

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The oil is then recovered fro
m alcohol by.
• Fractional distillation
• Evaporation under vacuum
• Dilution with water saturate
d with sodium chloride.
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Extraction using non volatile solve
nts
Pneumatic method
A current of warm air is passed through the
flowers. The air laden with essential oils i
s passed through a spray of
melted fat in a closed chamber in which th
e oil is absorbed.
The oil is
recovered as
above.
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Maceration method
The flowers are soaked in hot
oil to have their cell
membranes ruptured, the hot
oil then absorbs the essence.
Exhausted flowers are
removed and replaced by new
ones. The oil is recovered as
above
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Supercritical fluid
extraction

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Supercritical fluid extraction

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 Supercritical fluid extraction
• The use of super-critical carbon dioxide extraction is
a new way to extract essential oils from botanical ma
terial and although a bit on the expensive side, doe
s yield good quality oils
• Carbon dioxide becomes hypercritical at 33 oC, whic
h is a state in which it is not really gas or liquid, but h
as qualities of both, and is an excellent solvent to u
se in the extraction of essential oils since the low te
mperature required and the fact that the process is
near to instantaneous. 52
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Enzymatic hydrolysis followed by stea
m distillation.
For Essential oils occur in glycosidal com
bination:
• Methyl salicylate (gaultherin) in wintergre
en
• Eugenol (gein) in Geum urbanum
• Benzaldehyde (amygdalin) in bitter almo
nd
• Allyl isothiocyanate (sinigrin) in black m
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 Preparation of essential oil of bitter alm
ond
OC12 H21O10 Amygdalase &
CHO
CH Emulsin
CN + HCN + 2C H O
6 12 6

Amygdalin benzaldehyde glucose

2HCN + Ca(OH)2 Ca(CN)2 + H2O

3Ca(CN)2 + FeSO4 Ca2Fe(CN)6 +CaSO4

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• Detection of HCN in essential oil of bitter al
mond
Oil + NaOH aqueous layer +FeSO
4(+Fe3+)

+HCl ∆ Fe4{Fe(CN)6}3
Prussian blue color (+ve
HCN)
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 Preparation of essential oil of black mu
stard
S.C 6H11O5
CH2=CH.CH2N=C Myrosin
CH2=CH.CH2N=C=S + KHSO4 ++C6H12O6
O.SO3K

Sinigrin allyl isothiocyanat

e

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 Quality control for drugs containing esse
ntial oils and quality control of essential
oils
• Determination of essential oil percentage in t
he plant
This quantitative determination
is carried out by steam distillation
in special apparatus. The oil
volume is read and %V/W
is calculated.
(Clavenger apparatus) 60
 Determination of essential oil
percentage in the plant

 European Pharmacopoeia
Recovery of the distillate is
collected in the graduated
tube which already contains
a known amount of xylene
Vol. of E. oil =
total vol.- vol. of xylene
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 Quality control of essential o
ils
Physical Examination (measurements)
Odor
Solubility
Weight per ml
Melting point
Optical rotation
Refractive index
Analysis of the essential oils by chromato
graphic techniques (Gas chromatograph 62

y).
 Refractive index
Sin of the angle of incidence= refractive index
Sin of the angle of refraction

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 √ Gas chromatography
Is the most suitable analytical method (qu
alitative and quantitative analysis).

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Gas chromatography

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 Storage of essential oils
 Storage in well-closed containers
To minimize:
volatilization
exposure to air
absorption of moisture
Various change may result from exp
osure to light

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Protection of oils from light
by the use of amber- colored bottle
to prevent oxidation, hydrolysis, and polymeriza
tion
Storage in a cool place
to minimize oxidation and volatilization.
Rectification of essential oils:
Purification by re-distillation in order to r
emove non vol. matter and to adjust th
e proportion of the constituents to the
official standard.
"double-distilled" to produce oil of sta 68
Protection of oils from light
by the use of amber- colored bottle
to prevent oxidation, hydrolysis, and polymeriz
ation
Storage in a cool place
to minimize oxidation and volatilization.
Rectification of essential oils:
Purification by re-distillation in order to
remove non vol. matter and to adjust
the proportion of the constituents to t
he official standard.
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