Topic 12

Chemistry of Fragrance

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 Odors in Nature
 Living organisms use the chemical senses as a means of communication.

 Chemicals used to convey a signal from one organism to another are known as
semiochemicals.

 Semiochemical communication can be divided into two broad classes:

Pheromone
 A chemical emitted by an organism that influences the physiology or behavior of an
organism of the same species is known as a pheromone. (intraspecific interactions)
- Pheromones are similar to hormones but work outside of the body
- Pheromones induce activity in other individuals, such as sexual arousal

Allelochemical
 Chemical emitted by an organism that influences the physiology or behavior of an
organism of a different species is known as an allelochemical (interspecific
interactions). 2
Semiochemicals are volatile chemical
substances which contains specific
information to the recipient.

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 Pheromone

(1) alarm pheromones:

used by social insects in case of
attack by predators

(2) sex pheromones:

released by an organism to attract
an individual of the opposite sex,
encourage them to mate with them

(3) aggregation pheromones:

used for mate selection, defense
against predators, and overcoming host
resistance by mass attack.
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 Pheromone
(4) trail pheromones:
serve as a multi purpose chemical secretion in which, it leads members of its own
species towards a food source, while representing a territorial mark in the form
of an allomone to organisms outside of their species.

• Ants mark their paths with these pheromones, which are volatile hydrocarbons.
• Certain ants lay down an initial trail of pheromones as they return to the nest with
food. This trail attracts other ants and serves as a guide.
• As long as the food source remains, the pheromone trail will be continuously
renewed.
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• The pheromone must be continuously renewed because it evaporates quickly.
 Allelochemicals
• Allelochemicals are signals that travel from one animal to some member of a
different species. These include defensive signals such as repellents,
compounds used to locate suitable host plants, and a vast array of other substances
that regulate interspecific behaviors.

• Allelochemicals can be further subdivided into three groups based on who "benefits"
from the meassage: Synomones, Allomones, Kairomones

Synomones benefit both sender and receiver -- such as plant volatiles that attract
insect pollinators.

Synomones are beneficial to both

producer and recipient. For example, pine
trees damaged by beetles often emit
terpenes that attract parasitoid insects that
parasitize the pest beetles.
 Allelochemicals

Allomones benefit the sender -- such as a repellent, or defensive compound (e.

g. cyanide) that prevents predation.

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 Allelochemicals
• The grasshopper Poekilocerus bufonius feeds solely on plants of the
Asclepiadaceae, or milkweed, family.
• The milkweeds manufacture compounds known as cardenolides, toxins that can
severely disrupt normal cardiac function.
• When this grasshopper is attacked by a potential predator, it can defend itself by
ejecting a spray from a poison gland.
• Analysis of this fluid reveals that it contains two major cardenolides, calactin
and calotropin, both of which can also be extracted from the milkweeds on which
the grasshopper feeds.
Allomones benefit the sender

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 Allelochemicals

Kairomones benefit the receiver -- such as an odor that a parasite uses to find its
host.

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 Biosynthesis

• All living organisms produce chemicals through a process known as

biosynthesis.

• The material thus produced can be classified into two major groups, primary and
secondary metabolites.

• Primary metabolites: proteins, carbohydrates, lipids and nucleic acids (required for
metabolism).

• Allelochemicals are a separated group of secondary metabolites, which are not

required for metabolism (i.e. growth, development and reproduction).
Allelochemicals are plant defense against herbivory (An animal that feeds chiefly on
plants)

.
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 Biosynthesis
• The materials used as perfume ingredients are mostly secondary metabolites.

• The four categories of secondary metabolites, in decreasing order of importance as

sources of perfumes ingredients are terpenoids, shikimic acids derivatives,
polyketides and alkaloids. Among them, terpenes are the most important. The
higher the number of carbon atoms, the lower is the volatility of compounds.

• Monoterpnenes (C10) are more volatile, less persistence than the sesquiterpenes
(C15).

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 Extraction of natural Perfumes Ingredients

Three basic classes:

- Expression
- Distillation
- Solvent extraction.

Expression

- is the simplest of the three techniques.

- When odorants are forced out of the natural source by physical pressure, the
process is referred to as expression and the product is called an expressed oil.

-Example: If a piece of orange peel is squeezed, the oil bearing glands burst and eject
a fine spray of orange oil.
Many commercially available citrus oils are prepared in this way.
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Extraction of natural Perfumes Ingredients

3 Methods for Distillation

- Dry distillation

- Steam distillation

- Hydrodiffusion.

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 Extraction of natural Perfumes Ingredients
Dry distillation

Dry distillation is the heating of solid materials to produce gaseous products

which may condense into liquids or solids).
This method usually requires higher temperatures than classical distillation.

• Heat (direct flame) is applied to the surface of the vessel containing the plant
material. This technique is used for the oils of highest boiling point, typically
those derived from wood, because the high temperatures are necessary to vaporize
their chemical components.

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 Extraction of natural Perfumes Ingredients
Steam distillation

• Water or steam is added to the still pot and the oils are co-distilled with the
steam.

• The essential oil is separated from the water based on their differing densities.

• The waters that co-distil with the oil are called the waters of cohobation. They
can be separated by gravity according to their density. In most cases, these are a
waste product and are either discarded or recycled to the still pot.

• Rose oil is water soluble and kept as a perfume and flavor ingredient.

• The presence of water in the pot during steam distillation limits the temperature
of the process to 100 C.

• Much less degradation occurs in this process than in dry distillation. 15

Extraction of natural Perfumes Ingredients

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 Extraction of natural Perfumes Ingredients
Hydrodiffusion

It is a steam distillation
carried out upside down
since the steam is
introduced at the top
of the pot and the
water and oil taken off
as liquids at the bottom.

Perfume materials
obtained in this way are
referred to as essential
oils.

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 Extraction of natural Perfumes Ingredients

• Hydro diffusion method for extraction of oils is a type of steam distillation and is
only different in the way in which steam is enters the container of the still.

• In hydro diffusion, steam is fed in from the top onto the botanical material
while in the case of steam distillation, steam is fed from the bottom. In this way
the steam can saturate the plants more evenly.

• The condensation of the oil containing steam mixture occurs below the area in
which the botanical material is held.

• The main advantage of this method over steam distillation is that less steam and
shorter processing time is used. Therefore it produced a higher oil yield. This
method is also less harsh on the botanical material.

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 Extraction of natural Perfumes Ingredients
Solvent extraction

• The traditional solvent for extraction was benzene, but due to toxic effects of
benzene, petroleum ether, acetone, hexane and ethyl acetate, together with
various combinations of these, are typical solvents used for extraction.

• There has been a great interest in the use of liquid carbon dioxide as an extraction
solvent, referred to as super-critical carbon dioxide extraction.

• The pressure required to liquefy carbon dioxide at ambient temperature is still

considerable and thus the necessary equipment is expensive.

• This is reflected in the cost of the oils produced, but carbon dioxide has the
advantage that it is easily removed and there are no concerns about residual solvent
levels.

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 From Natural to Synthetic

• The development of organic chemistry in the 19th century began to make synthetic
chemicals available and their use in fragrances began to grow.

• The incorporation of synthetics into perfumery received in 1921 when COCO Chanel
launched her famous perfume, No 5. Chanel No5 owes its unique character to the
inclusion of synthetic aliphatic aldehydes, 2- methylundecanal in particular.

• The synthetic materials were cheaper to produce than natural materials. More
robust to survive in acidic, basic and even oxidizing media.

• It became possible to put perfume into household products in which natural oils
could not be used because of degradation of their components and resultant
changes in odour and colour.

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2- methylundecanal
 Applications of perfume

• The use of essential oils is also restricted by their chemical stability.

• Many of the components of natural oils do not survive in products such as

bleaches, laundry powders and even soaps.

• For example, the major component in jasmine oil is benzyl acetate, which is
hydrolysed in all of these products owing to their high pH (13-14, 10-11 and 9-10)
and it is also susceptible to the oxidants. The indole present in jasmine causes
soap to discolour.

benzyl acetate 21
 Applications of perfume

Fine Fragrance

• The Business Scents Eau de Parfurm formulation contains 78% denatured ethanol.

• The source of this ethanol (e.g. synthetic; or natural grain starch, sugar beet, or
molasses alcohol) can give rise to a different odour in the end product, and thus it is
important to know what type of alcohol is likely to be used.

• Denaturants (which prevent people from ingesting the alcohol) are required by
legislation in many countries and are also useful to know, although less likely to have
a significant effect on the finished product.

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 Applications of perfume

Preparation

Blend the fragrance and ethanol, then add the water and remaining ingredients slowly
with mixing.

Allow to mature at room temperature for up to 10 days and then cool to + 1 C, followed
by filtration.

A filter aid, such as magnesium carbonate at 0.2% can be used to remove difficult
precipitates.

Fill into clean, glass bottles.

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 Applications of perfume

• In this case, a standard 99.7% v/v synthetic grade, containing 0.1% v/v ter-
butanol as a marker and denatured with 10 ppm of Bitrex [INCT name is
denatonium benzoate, an extremely bitter substance], is likely to be used by the
client.

• The formulation also contains an ultraviolet (UV) radiation absorber,

benzophenone-2, to prevent degradation of the fragrance and any dyes by light.

• Although consumers are encouraged to keep fine fragrances in the dark, the
manufacturer needs to protect the product from those of its customers who insist
on storing it on a sunny window shelf.

• A moisturizing ingredient which has additional fragrance fixative properties

(PPG-20 methyl glucose ether) is also incorporated in this instance.

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