Prof. Hala M.

Hammoda

PHYTOCHEMISTRY

Lecture (4), 17/10/2012:

"VOLATILE OILS"
"Essential Oils" "Ethereal Oils"

Definition:

The volatile oil is obtained by the steam distillation of plants or by other

means then by direct steam distillation.
All volatile oils are obtained from plant source except oil of Musk, from Male
deer and Amber, from whale.

Fixed oils Volatile oils

Can not be distilled from their natural Can be distilled from their natural
sources. sources.
(Capable of volatilization)
Leave a permanent Do not leave
grease spot on paper. a permanent grease spot.
Consist of glyceryl esters of fatty Do not consist of glyceryl esters of
acids. fatty acids.
Can be saponified with Cannot be saponified with alkalis.
alkalis.
Become rancid Do not become rancid upon long
(be rotten) upon long storage. storage.
Instead on exposure to light and air,
they become oxidized and resinified.

Occurrence of V.O. in plant tissues:

1- In all tissues of the plant (Pinaceae) (‫)الصنوبر‬

2- Localized in one or more organ of
the plant, e.g.

- Petals of flowers (Rose)

- Barks and leaves (Cinnamon)

- Pericarp of fruits (Umbelliferous fruits)

- Stems and leaves glandular hair (Mentha)

- Petals and rind of fruits and leaves (Orange)
Prof. Hala M. Hammoda

Combination of Volatile Oils in the plants:

Volatile oils may combine with a sugar part to form a glycoside.

Volatile oils may combine with:
Gums 99. Oleo-gums
Resins 99. Oleo-resins
Both 99. Oleo-gum resins

Why do plants synthesize V.O.?

Physiological significance
Some scientists think that volatile oils are waste products, not formed to
serve any biological function.
Several ecological theories state that plants synthesize V.O. to use them for:
• Attraction of insects.
• Defense agents.
• Solvents for wound-healing resins.
• A way of eliminating certain abnormal metabolic products
(Detoxification products).

Medicinal and commercial uses of V.O:

Therapeutic uses (Aromatherapy): External application and internal

application.

Perfume industries, Cosmetics and Soap manufacture.

Spices and Condiments with preservative action.

Flavoring agents for pharmaceutical industries (Medication for infants),
food and tobacco.

Therapeutic uses of V.O:

A- External application:

Because of the lipoid solubility of V.O., they are easily resorbed through
the skin and mucosa:

(1) Hyperaemic effect:

V.O cause a better local blood circulation on the applied area and may
influence the inner organs. (ex. Cardiac ointments for relief of pain in some
cases of angina pectoris).

Depending on the degree of skin-irritation:
- Rubefacients cause only an increased blood circulation and it can be
observed as redness of the skin. ex. Eucalyptus oil, gaultheria oil and
camphor oil.

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Prof. Hala M. Hammoda

Used to relieve various skeletal muscles pains in form of:

liniments, tinctures, extracts, oils for bath, ointments and gels.
- Vesicants cause stronger skin irritation and may even cause blisters.

(2) Anti-inflammatory effect:

There are many reasons for this effect of essential oils, the antimicrobial
action of essential oils is also an important aspect of their anti-inflammatory
effect. ex.

Chamomile oil containing matricin, and chamazulene.

Arnica flower oil containing thymol.

(3) Antiseptic effect:

Mechanism of action of V.O as antiseptic:
V.O have lipoid solubility and it can dissolve the fats on cell wall of bacteria.

Phenol coefficient:
It measures the bactericidal activity of a compound in relation to phenol (=1).
The higher the phenol coefficient value, the more effective the disinfectant. A
value greater than 1 means that the disinfectant is more effective than
phenol. Examples:
Thyme oil → phenol coeff. = 13.2
Thymol → phenol coeff. = 20.6
Chlorothymol (synthetic) → phenol coeff. = 75

(4) Deodorizing effect:

Best known is the deodorizing effect of chamomile preparations.

In surgery after an accident,
chamomile extracts are used in
a bath in order to clean large wounds.

Deodoration of malodorous wounds are carried out with rectified citrus
oils, rectified turpentine and thyme oil.

B-Internal applications:

Essential oils are usually getting quicker into the blood-circulation by
inhalation than by oral application:

(1) Expectorating effect:

Due to: a- Secretolytic effect (lysis of secretion).
b- Secretomotor effect (moving the secretion).

Volatile oil has a little broncho-spasmolytic effect (relief broncospam).

Example: Camphor, Menthol, Anise, Thyme oil.

(2) Stimulation of secretions of digestive glands:

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Prof. Hala M. Hammoda

Essential oils are used because of their appetite stimulation, this is done by
stimulating the secretion of saliva and gastric enzymes and stimulating the
secretion of bile (choleretic effect).
(3) Carminative effect:
Anise fruits oil, basil, fennel, chamomile, coriander, caraway fruits, and
peppermint oil.

(4) Spasmolytic effect:

It is observed as relief of spasms of smooth muscles of intestines and gall
bladder. ex. Chamomile, caraway, fennel, orange and peppermint oil as well
as cinnamon oil.

5) Circulation stimulating effects:

Some V.O. has stimulating effect on the respiration and circulation centers.
Ex: Camphor, rosemary, lavender and peppermint oils.

Undesirable side effects of V.O:

1- Allergic effect:
V.O. have no allergic effect but upon storage, terpene hydrocarbons (contain
double bonds) (have no allergic effect) will be converted into terpene
hydroperoxides (have allergic effect).

2- Phototoxic and photosensitizing effect:

Some V.O. containing furanocoumarins (are used in the treatment of vitiligo)
can after an initial photosensitizing effect.
They give phototoxic reactions which can be observed as erythema
(Redness of the skin, caused by hyperemia, increase of blood flow) and
formation of blisters.

3- Abortion provoking effect:

The uterus stimulating effect of some essential oils has been and is still
misused for abortion. Essential oils cause distinct filling of blood vessels of
the pelvis and strong contraction of the uterus. Misuse of essential oils may
be fatal.
ex. High doses of thujone containing essential oils as junipers (‫)العرعر‬,
chenopodium oil and parsley fruit (‫ )البقدونس‬oil.

4- Carcinogenic effect:

β-asarone has a chromosome-damaging effect on human lymphocytes
(white blood cell).

Carcinogenic activity (liver carcinoma) may also be caused by safrole
(the main component of sassafras oil, used as spice it has lemon odor). In
some countries safrole is not permitted in food.

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Prof. Hala M. Hammoda

Estragole (methyl chavicol) is the main constituents of one of the

varieties of fennel oil known as bitter fennel oil. Estragole has carcinogenic
and mutagenic effect. It is important to avoid the use of estragole - rich
chemotypes of fennel particularly for small children.

Methods of preparation of V.O:

1. Hydrodistillation.
2. Scarification and expression.
3. Extraction with solvents.
4. Enzymatic hydrolysis.
5. Supercritical methods.

The choose of the method depends on:

1. The condition of the plant material.
2. The location of the oil in the plant.
3. The amount of the oil.
4. The nature of the constituents of the oil.

This method is based on the fact that a mixture of water and immiscible liquid
(V.O.) boils at a temperature lower than water. ex. The boiling point of
turpentine oil is about 160°C, but on mixing with water and heating, the
mixture boils at about 95.6°C.
The principle of these methods is that, the boiling water or steam penetrate
the plant tissue and vaporizes all volatile substances.

Before distillation the plant material must be subjected to size reduction

in order to expose a great number of oil glands. This process termed
"Comminution". Flowers, leaves and other thin and non-fibrous parts of the
plant can be distilled without comminution. Seeds and fruits must be crushed.
Roots, stalks and all woody materials should be cut into short length.

There are three types of hydrodistillation:

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Prof. Hala M. Hammoda

a- Water distillation:

The plant material is mixed directly with water in a still pot.

b- Water and steam distillation:

The plant material is supported on a perforated grid screen inserted some

distance above the bottom of the still. prevent direct water contact with the
plant material.

c- Direct steam distillation:

No water is kept in the bottom of the still.

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Prof. Hala M. Hammoda

The oil separator:

The mixture of the oil and water is passed through condenser, then oil is
separated from the aqueous layer and can be isolated, usually by use of a
Florentine receiver. There are 2 types of Florentine receiver:

Disadvantages of the distillation method:

1-The high temperature in the presence of water during distillation induce

hydrolysis of esters and removal of water from tertiary alcohols.

2- Loss of water soluble components of V.O.

3-Volatile amines and volatile degradation products of carbohydrates

(furfural) pass over during distillation and contaminate the V.O.
The distillation water contains small amounts of dissolved volatile oil and is
often returned to the distillation still in order to recover the dissolved oil. This
process is called Cohobation (Redistillation of water).

Used for volatile oils:

 Cannot be distilled without decomposition (sensitive to heat,
thermolabile).
 Found in large amount in oil - glands just below the surface in the
peel (rind). Generally, they are obtained by expressing the rind of the
fresh fruit. ex. oil of orange and lemon.

a) The sponge method:

-The citrus fruit is washed, cut into halves. and the juicy part is removed. The
rind is turned inside out and squeezed. When secretion gland rupture and
the oil is collected by means of the sponge. When the sponge becomes
saturated, it is squeezed in a vessel and the oily layer is separated from the
aqueous layer.

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Prof. Hala M. Hammoda

b) écuelle à piquer method (Scarification):

- The entire fruits are rotated in metal pins with sharp projections just long
enough to penetrate the epidermis puncturing oil cells to exudate the oil.

Used for volatile oils:

 Containing labile constituents (sensitive to heat).
 Present in extremely small quantities ex. in the flowers of jasmine,
violet, roses (Perfumes).

a) Using volatile solvent:

Usually light petroleum is used by percolation.

b) Using non- volatile solvent:

i. Enfleurage method (Extraction with cold fat):

The principles of enfleurage:
Certain flowers continue the physiological activities of developing and giving
off perfume even after picking. ex. Jasmine flowers. Fat possesses a high
power of absorption of the perfume emitted.
- In the enfleurage process, a fat base (lard) “Corps” is spread in a thin layer
on both sides of a glass plate supported on a rectangular wooden frame
"Chassis". Batches of fresh flowers are lightly layered over the fat base.
Several chassis are placed one above the other so that the flowers get
sandwiched between two layers of fat which absorbs the perfume as it is
given off.
Exhausted flowers are removed and called "De flèurage" and replaced by the
fresh flowers until the fat is relatively saturated with flower oil.
The perfumed fat must then be removed from the glass plates, and called
“Pomade".
The most highly saturated pomade being "Pomade 36" means the chassis
has been treated with fresh flowers 36 times during the whole process of
enfleurage.
The pomade is then extracted three times with alcohol 95% "Triple
extraction", the obtained solution known as "extracts". The extract is
concentrated at low temperature till free from alcohol, the concentrated flower
oil is called "Absolute of enfleurage", "Absolute of pomade" or
"Liquid concretes".

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Prof. Hala M. Hammoda

ii. Extraction with hot fat:

The physiological activities of some flowers, ex. roses, are stopped by
picking. So, the flowers are extracted by immersion in hot fat (their cell
membranes ruptured then the hot oil absorbs the essence). The same batch
of hot fat is treated with several batches of fresh flowers until the fat becomes
quite saturated.

The volatile oil may found in the plant in a glycosidal form, the odoriferous
substance is released only by hydrolysis:
Bitter almond oil:

Winter green oil:

Black mustard oil:

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Prof. Hala M. Hammoda

Clove oil:

Supercritical fluid extraction (SFE)

Separating any essential oil from the matrix using supercritical fluid as
extracting solvent, ex. SC CO2.

Prof. Hala M. Hammoda

Pharmacognosy Department
Faculty of Pharmacy
Alexandria University

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