ESSENTIAL OILS
MARIYA A JAISON
OST-2021-24-15
What are essential oils
● According to International Standard Organization on Essential Oils(ISO 9235:2013) and the
European Pharmacopoeia ( Council of Europe) an essential oil is defined as the product obtained
from plant raw material by hydrodistillation, steam distillation or dry distillation or by a suitable
mechanical process (for citrusfruits)
● The definition of an essential oil excludes other aromatic/volatile products obtained by different
extractive techniques like extraction with solvents (con-cretes, absolutes), supercritical fluid
extraction, and microwave-assisted extraction.
● Essential oils also differ from fixed oils or fatty oils in both chemical and physical properties. Fatty
oils contain glycerides of fatty acids and leave a permanent stain on filter paper, whereas essential
oils contain volatile compounds and vanish rapidly without leaving any stain.
● Essential oils are complex mixture of volatile to semi volatile compounds, usually
with a strong odor, rarely coloured, soluble in organic solvents and insoluble in water
● They comprise of volatile compoumds of terpenoid and nonterpenoid origin,
synthesized through different biosynthetic routes and with distinct primary metabolic
precursors.
● An essential oil is essential in the sense that it contains the essence of the plant's
fragrance—the characteristic fragrance of the plant from which it is derived. It is
secondary metabolite of plants
ESSENTIAL OILS CHEMICAL CONSTITUENTS
❏ There are two main groups of metabolites that can be found in nature:
primary and secondary metabolites.
❏ Primary metabolites are universal compounds, present in all living organisms,
and include proteins, carbohydrates, lipids, and nucleic acids.
❏ Secondary metabolites are found only in some species and are classified as
terpenoids, shikimates, polyketides, and alkaloids. EOs are composed of
different chemical compounds.
❏ The constituents of plant EOs fall mainly into two distinct chemical classes:
terpenes and phenylpropanoids.
❏ Terpenes and their oxygenated derivatives (terpenoids) are more frequent and
abundant in EOs, certain species contain high quantities of shikimates;
namely, phenylpropanoids, and they provide a specific odor and flavor to the
plant
❏ Pure essential oils are mixtures of more than 200 components, normally
mixtures of terpenes or phenylpropanic derivatives, in which the chemical and
structural differences between compounds are minimal.
❏ Volatile fraction: Essential oil constituting of 90–95% of the oil in
weight,containing the monoterpene and sesquiterpene hydrocarbons, as well as
their oxygenated derivatives along with aliphatic aldehydes, alcohols, and
esters.
❏ Nonvolatile residue: that comprises 1–10% of the oil, containing hydrocarbons,
fatty acids, sterols, carotenoids, waxes, and flavonoids.
AROMA OF ESSENTIAL OILS
❏ Terpenoid and phenylpropanoid derivatives are the main components
found in essential oils.
❏ In most plants, their essential oils contain terpenoids at around 80%.
But the presence of phenylpropanoid derivatives affords the essential
oils significant flavor, odor.
❏ These two groups of compounds are derived from two different
pathways from different primary metabolites
CLASSIFICATION
EOs can be classified into the three main groups:
● Terpenes, related to isoprene
● Phenylpropanoids (benzene derivatives)
● Miscellaneous group having varied structures not included in first three groups (sulfur‐ or
nitrogen‐containing compounds)
1. TERPENES
❏ Essential oils constituents can be divided into two major groups: terpene
hydrocarbons and oxygenated compounds
❏ Terpenes and terpenoids result from the condensation of isoprene (2-
methyl-1,3-butadiene), a pentacarbonate unit with two unsaturated bonds,
and therefore are many times called isoprenoides
❏ They have many isomeric cyclic or linear structures, and various degrees of
unsaturations, substitutions, and oxygenated derivatives, generally called
terpenoids
TERPENE HYDROCARBONS
❏ Terpenes are the most common class of chemical compounds found in essential
oils
❏ Terpenes are synthesized in the cytoplasm of plant cells, through the mevalonic
acid pathway
❏ Terpenes have been regarded as polymers of isoprene (C5H8) joined in a
repetitive head‐to‐tail manner
STRUCTURE OF TERPENE
CLASSIFICATION OF TERPENES
● They could be classified according to the fusion of the isoprene units or to the number of the
rings.
● Terpenes can be classified into hemiterpenes (1 unit), monoterpenes (2 units), sesquiterpenes
(3 units), diterpenes (4 units), sesterterpenes (5 units), triterpenes (6 units) and polyterpenes
(many units).
● The combinations of two isoprene units are called a “terpene unit.”.
● Monoterpenes (C10H16) are formed by the attachment of two isoprene units (at least one
double bond).
● These terpenes have a hydrocarbon skeleton which can be rearranged into acyclic, cyclic, or
aromatic.
● Cyclic monoterpenes can be classified according to their ring size such as monocyclic
monoterpenes, bicyclic monoterpenes and tricyclic monoterpenes.
● These compounds oxidize easily because of their rapid reaction to air and heat sources.
CHEMICAL STRUCTURE OF ACYCLIC AND MONOCYCLIC TERPENES
CHEMICAL STRUCTURE OF BICYCLIC AND TRICYCLIC TERPENES
SESQUITERPENES
● Sesquiterpenes (C15H24) are the second to the dominant monoterpenes.
● They are formed from the combination of three isoprene units
Sesquiterpenes are unsaturated compounds.
● There are linear, branched, or cyclic sesquiterpenes.
● Sesquiterpenes are unsaturated compounds. Cyclic sesquiterpenes can
be classified into monocyclic, bicyclic, or tricyclic.
● Diterpenes are formed by the head‐to‐tail combinations of four isoprene
units followed by rearrangement and/or substitutions.
CHEMICAL STRUCTURE OF ACYCLIC AND
MONOCYCLIC SESQUITERPENES
CHEMICAL STRUCTURE OF BICYCLIC AND TRICYCLIC SESQUITERPENES
❖ They are important components of plant resins
❖ Diterpenes, triterpenes and tetraterpenes are present at a very low
concentration in essential oils.
❖ Their recovery increases with increasing steam distillation times
and influenced by the extraction method.
OXYGENATED COMPOUNDS -TERPENOIDS
The oxygenated compounds are grouped as (esters, aldehydes, ketone,
alcohols, phenols and oxides), and consists of a combination of carbon,
hydrogen and oxygen atoms. Scientists have identified more than 3,000
compounds.
● Alcohols:
Alcohols have a great importance in the perfume industry, for example; monoterpene
alcohols like, linalool found in coriander, terpinen-4-ol found in Marjorana hortensis ,
menthol in peppermint oil , geraniol and citronellol in rose oil, borneol in rosemary oil,
sesquiterpene alcohols like α-bisabolol in chamomile, α-santalol in sandalwood oils; and
diterpene alcohols such as phytol found in coriander, manool and scareol found in Salvia
officinalis and Salvia sclarea, respectively.
● Phenols
The major monoterpene phenols like thymol and carvacrol found in thyme, Eugenol in
basil
● Aldehydes:
Such as citral, found in citrus lemon grass oils also geranial and citronellal in lemon balm
● Ketones:
Monoterpenoid ketones are cyclic compounds produced by oxidation of alcohols.
Monocyclic ketones such as carvone in caraway seed oil, bicyclic ketones like camphor found in
(Cinnamomum camphora),Thujone from sage (Salvia officinalis) and isopinocamphone is the main
constituent of oil of hyssop Hyssopus officinalis
● Esters:
Linalyl acetate in lavender oil ; neryl acetate and geranyl acetate in Dracocephalum moldavica.
● Ethers:
Like anethole found in aniseed , and safrole found in star anise
● Lactones and coumarins:
Sesquiterpene lactones consist of one and half terpenes (or six isoprene units) attached to
a lactone ring like coumarins, such as furocoumarin – bergapten in bergamot oil.
PHENYLPROPANOIDS
❏ It contains one or more C6-C3 fragments, The C6 unit being a benzene ring.
❏ Most plant families contain these compounds are Apiaceae, Lamiaceae, Myrtaceae,
and Rutaceae families.
❏ Examples of these compounds in volatile oils are enethole in anise and fennel.
❏ Apiol in celery and parsley, Eugenol in clove, Methyleugenol found in rose oil,
Methylchavicol in basil, Myristicin in parsley.
❏ Phenylpropanoids are synthetized via the shikimic acid pathway
Sulfur-containing compounds:
● Plants such as garlic and onion contain volatile sulfur compounds, namely allyl sulfide,
dimethylthiophene, dimethyl sulfide, allicin, diallyl disulfide, diallyl trisulfide and also,
allyl isothiocyanate; butyl isothiocyanate;
● Butenyl isothiocyanate,allyl disulfide and phenylethyl isothiocyanate found in Brassica
rapa var. rapifer
Nitrogen-containing compounds:
● Methyl anthranilate present in several citrus oils
● Hexanedinitrile and Benzenepropanenitrile found in Brassica rapa var. rapifera
Sulphur and nitrogen containing compounds:
● 4-methylthiobutyl-isothiocyanate (Erucin); 5-methylthio-pentanonitrile from the leaves
of Eruca sativa essential oil
BIOSYNTHETIC PATHWAYS
● Terpenoid and phenylpropanoid derivatives are the main components found in
essential oils.
● In most plants, their essential oils contain terpenoids at around 80%. But the
presence of phenylpropanoid derivatives affords the essential oils significant flavor,
odor.
● These two groups of compounds are derived from two different pathways from
different primary metabolites.
MEVALONATE PATHWAY
● Terpenoid molecules are created by the mevalonic acid pathway.
● The steps of this pathway include the creation of mevalonic acid with six carbon
atoms the rearrangement of mevalonic acid by a series of enzymatic
transformations to form isopentenyl pyrophosphate, which consists of a branched
five-carbon molecule (an isoprene unit); and the joining of isoprene to two
phosphate groups
● Isoprene is the main constituent of EOs that starts the manufacture of terpenoid
compounds
SHIKIMIC ACID PATHWAY
❏ Phenylpropanoids are synthetized via the shikimic acid pathway, their main
precursors being cinnamic acid and p-hydroxycinnamic acid, originated from the
aromatic amino acids phenylalanine and tyrosine, respectively
❏ Shikimic acid is synthesized from erythrose 4-phosphate and phosphoenolpyruvate.
❏ Moreover, aromatization of shikimic acid gives benzoic acid derivatives, present in
several essential oils
METHODS OF EXTRACTION
● Essential Oils are not made, but instead, they are extracted from plant materials. Extractions
are used to obtain a plant’s active botanical constituents that function as its “life force.”
● They are essentially the liquefied version of a plant, and they effectively allow its beneficial
compounds to reach the bloodstream faster than they would by simply consuming the plant.
STEAM DISTILLATION
Steam Distillation is the most popular method used to extract and isolate essential oils
from plants for use in natural products. This happens when the steam vaporizes the plant
material’s volatile compounds, which eventually go through a condensation and
collection process.
STEAM DISTILLATION PROCESS
● A large container called a Still, which is usually made of stainless steel, containing the plant
material has steam added to it.
● Through an inlet, steam is injected through the plant material containing the desired oils,
releasing the plant’s aromatic molecules and turning them into vapor.
● The vaporized plant compounds travel to the condensation flask or the Condenser. Here, two
separate pipes make it possible for hot water to exit and for cold water to enter the Condenser.
This makes the vapor cool back into liquid form.
● The aromatic liquid by-product drops from the Condenser and collects inside a receptacle
underneath it, which is called a Separator. Because water and oil do not mix, the essential oil
floats on top of the water. From here, it is siphoned off. (Some essential oils are heavier than
water, such as clove essential oil, so they are found at the bottom of the Separator.)
● Hydro distillation
Hydro Distillation has the risk is that the still can run dry, or be overheated, burning
the aromatics and resulting in an Essential Oil with a burnt smell. Hydro distillation
seems to work best for powders (i.e., spice powders, ground wood, etc.).
● HD has become the standard method of essential oil extraction from plant
material such as wood or flower, which is often used to isolate nonwater-
soluble natural products with high boiling point.
● The process involves the complete immersion of plant materials in water,
followed by boiling.
● This method protects the oils extracted to a certain degree since the
surrounding water acts as a barrier to prevent it from overheating.
● The steam and essential oil vapor are condensed to an aqueous fraction
● The advantage of this technique is that the required material can be
distilled at a temperature below 100 °C.
Mechanical extraction
● Expression is used to extract essential oils from citrus fruits. Expression is the
process of grating or scraping the peel of a citrus fruit to release the oils. For
example, when a lemon is squeezed the scent of lemon rises into the air because the
volatile oils have been released from sacs found in the peel.
● In the process of essential oil expression, care is taken to capture the oil. Expression
does not involve heating; thus, the chemistry of citrus essential oils is not heat-
altered and citrus oils smell very similar to the fruits from which they come.
APPLICATIONS
● EOs have various applications, mainly in the health, agriculture, cosmetics, and food
industries.
● In particular, the EOs of aromatic plants and spices have been used in food preservation
and as flavoring agents in food products, drinks.
● Perfumeries, and cosmetics, creams and in personal hygiene products.
● EOs are used as feed additives, antioxidants and growth promotors.
● Used in wound healing, rejuvenation and relaxing medicine.
● Used in aroma therapy including the inhalation, massage, masking agent to avoid the
unpleasant odor in the textile industries, paint and plastic industries.
● Essential oils are also used as the natural antifungal and antibacterial agents in the food
safety items.
● Essential oil also used in the various kinds of cereals, antimicrobial packing of the food
items, edible thin film, nanoemulsion, preservation of the fruits and vegetables, soft
drinks, as the flavoring agents in the carbonated drinks, as the major ingredients in
THERAPEUTIC USES
