Chemistry of

Fragrances and
Flavours
Mallari, Donna Joy
R.
ChE-4202

Smell is a potent wizard that transports

you across thousands of miles and all the
years you have lived.
-Helen Keller

FRAGRANCES

Fragrance
Indulgence
Pleasure
Luxury

Fragrance is a
sensory
pleasure and a
vital part of
brand
communication.

Scent is an
emotional
catalyst.

What is
Perfume?
Perfume is a mixture of
fragrant essential oil
and aroma compounds,
fixatives, and solvents
used to give the human
body, objects, and
living spaces a
pleasant smell.

The word perfume

comes from the Latin
per fumum, which
means through
smoke.
To the ancients,
burning perfumed
substances meant
communicating with lost
loved ones.

The Perfume we know and

use today, came about in Italy,
clear back in 1320. Italians
discovered and perfected a
technique for distilling alcohol.
Compared to other varieties of
scent, PERFUMES are longer
lasting on the skin and are
more expensive because they
contain greater percentage of
essential oils.

Today the production

of perfume is part of a
multi billion-dollar
industry. In ancient
times it also played a
major role in the
prosperous trading of
merchandise between
the east and the west.

Up until then,
perfumes were
produced with an
oil or animal fat
base and were
used as lotions
and pomades.

THE HISTORY OF AROMA

CHEMISTRY
AND PERFUME

Greece
By the 7th century
BC, Athens had
developed into a
mercantile center in
which hundreds of
perfumers set up
shop.

Greek Perfume Urns

France
16th & 17th centuries - Southern France (Grasse) becomes
a center of expertise for the growing, extraction and
distillation of essential oils.
France becomes the Perfume center of the world. Large
scale cultivation & processing of valuable plants for oils
such as rose soon was centered there. And raw materials
from around the world were imported for processing.
Extraction & distillation techniques were refined.

The Organic Chemist

Mid-1800s - From Germany
came a new breed of
Chemist that would
revolutionize industry and
bring an end to Alchemy.
This type chemist used the
scientific method to
unravel chemical structures
and create materials from
coal, petroleum and other
materials.

1855 First synthesis of cinnamaldehyde

1868 Commercial production of coumarin the first
synthetic fragrance chemical (Fougere Royale)
1874 Chemical structure of vanillin determined.
1876 Synthetic vanillin production starts.
1850 to 1900 Significant advances in elucidating major
chemicals in Essential oils.

Raw Materials
Natural ingredientsflowers, grasses, spices,
fruit, wood, roots, resins,
balsams, leaves, gums,
and animal secretions
as well as resources like
alcohol, petrochemicals,
coal, and coal tars are
used in the manufacture
of perfumes.

Aromatics Sources

Plant Sources
Plants have long been used in perfumery
as a source of essential oils and aroma
compounds.
These aromatics are usually secondary
metabolites produced by plants as
protection against herbivores, infections,
as well as to attract pollinators. Plants
are by far the largest source of fragrant
compounds used in perfumery.
The sources of these compounds may
be derived from various parts of a plant.
A plant can offer more than one source
of aromatics, for instance the aerial
portions and seeds of coriander have
remarkably different odors from each
other.

Bark: Commonly used barks includes cinnamon

and cascarilla. The fragrant oil in sassafras root
bark is also used either directly or purified for its
main constituent, safrole, which is used in the
synthesis of other fragrant compounds such as
helional.
Flowers & Blossoms: Undoubtedly the largest
source of aromatics. Includes the flowers of several
species of rose and jasmine, as well as osmanthus,
mimosa, tuberose, as well as the blossoms of citrus
and ylang-ylang trees.

Fruits: Fresh fruits such as apples, strawberries,

cherries unfortunately do not yield the expected odors
when extracted; if such fragrance notes are found in a
perfume, they are synthetic.The most commonly used
fruits yield their aromatics from the rind; they include
citrus such as oranges, lemons, limes, and grapefruit.

Leaves & Twigs: Commonly used for perfumery

are lavender leaf, patchouli, sage, violets,
rosemary, and citrus leaves. Sometimes leaves are
valued for the "green" smell they bring to perfumes,
examples of this include hay and tomato leaf.

Lichens: Commonly used

lichen includes oakmoss and
treemoss thalli.

Resins: Valued since antiquity, resins have

been widely used in incense and perfumery.
Highly fragrant and antiseptic resins and resincontaining perfumes have been used by many
cultures as medicines for a large variety of
ailments. Commonly used resins in perfumery
include labdanum, frankincense/olibanum,
myrrh, Peru balsam, gum benzoin.

Roots, rhizomes
and bulbs:
Commonly used
terrestrial portions in
perfumery include iris
rhizomes, vetiver
roots, various
rhizomes of the
ginger family.

Seeds: Commonly
used seeds include
tonka bean,
coriander, caraway,
cocoa, nutmeg,
mace, cardamom,
and anise.

Woods: Highly
important in providing
the base notes to a
perfume, wood oils
and distillates are
indispensable in
perfumery. Commonly
used woods include
sandalwood,
rosewood, agar wood,
birch, cedar, juniper,
and pine.

Animal Sources
Animal substances are often used as fixatives that
enable perfume to evaporate slowly and emit odors
longer. Other fixatives include coal tar, mosses,
resins, or synthetic chemicals.
Civet from civet
cat

musk from male

deer

ambergris from
the sperm whale

SYNTHETIC SOURCES

Synthetic aromatics are created through organic synthesis from

various chemical compounds that are obtained from petroleum
distillates, pine resins, or other relatively cheap organic
feedstock.

Synthetic aromatics are often used as an

alternate source of compounds that are
not easily obtained from natural sources.

Synthetics can
provide
fragrances
which are not
found in
nature.

For example, linalool and coumarin are

both naturally occurring compounds that
can be cheaply synthesized from
terpenes.

WHY?

This was because of the cost of

producing the natural materials
required as ingredients.

The synthetic materials were

cheaper to produce than natural
materials and their supply was much
more secured, thus making perfume
accessible to all.
The incorporation of
synthetics into perfumery
received a huge fillip in
1921 when Coco Chanel
launched her famous
perfume, No. 5. Chanel 5
owes its unique character to
the inclusion of synthetic
aliphatic aldehydes
alongside the natural oils
such as rose and jasmine.

The development of organic

chemistry in the nineteenth
century began to make synthetic
chemicals available and their use
in fragrances began to grow.

Furthermore, more robust molecules

could be produced, which would
survive in acidic, basic and even
oxidising media. Thus, 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.

INGREDIENTS FOR THE

MODERN
PERFUMERY INDUSTRY

PERFUME INGREDIENTS DERIVED

FROM TERPENOIDS
The terpenoids form the largest group of natural
odorants, so it is only to be expected that they
also form the largest group of modern fragrance
ingredients.
Thousands of different terpenoid structures
occur in perfume ingredients, both natural and
synthetic.
The most important members of the terpenoid
family for perfume materials are the oxygenated
monoterpenoids.

Important Terpenoid Fragrance Materials

Material

Odour

Amberlyn/Ambrox/Ambroxan

Ambergris

Carvone

Spearmint

Citronellol and esters

Rose

Dihydromyrcenol

Citrus,floral

Geraniol/nerol and esters

Rose

Hydroxycitronellal

Muguet

Borneol/isoborneol and acetate

Pine

Linalool

Floral, wood

Linalyl acetate

Fruit, floral

Menthol

Mint, coolant

(Methyl)ionones

Violet

Terpineol and acetate

Pine

Acetylated cedarwood

Cedar

Hemiterpenoids

A small number of hemiterpenoids are used in perfumery, the most

important of these are prenyl acetate and benzoate. Thioesters,
such as those shown in Figure 4.11, have extremely intense green
odours reminiscent of galbanum, in which they occur naturally. The
esters are usually prepared from prenyl chloride and the thioesters
from the corresponding thiol and acid chloride as shown in Figure
4.11.

Acyclic Monoterpenoids
The alcohols geraniol/nerol, linalool,
citronellol and their esters are the
largest tonnage materials of this
class.

Cyclic Monoterpenes
The three most important cyclic monoterpenoids are lmenthol, l-carvone and -terpineol (including its esters). lMenthol occurs in a number of mint oils and is used not
only for its minty odour, but also, and more importantly,
for its physiological cooling effect.

Carveol is one of the minor

components responsible for the
odour of spearmint. It is easily
prepared by reduction of carvone.
The phenols carvacrol
and thymol are
important in some herbal
odour types, but the
major use for thymol is
as a precursor for
menthol q.v.

Isopulegol is prepared
from citronellal, as
discussed in the section on
menthol, and is a precursor
to other materials in the
group.

Piperitone and pulegone are strong

minty odorants. The latter is the major
component of pennyroyal oil.

Menthofuran is a minor
component of mint oils and can
be prepared from pulegone,
though normally, its presence in
mint is undesirable because of
its odour properties.

1,8-Cineole is the major

component of such
eucalyptus oils as
Eucalyptus globulus. These
oils are inexpensive and so
there is no need to prepare
cineole synthetically.

PERFUME INGREDIENTS
DERIVED FROM BENZENE

One of the most important perfume

ingredients made from benzene is 2phenylethanol. The synthesis of this, and
related compounds, is shown in Figure
4.62.
2-Phenylethanol is a major component of
rose oils and is widely used in perfumery
for its blending qualities. The original
production method involved FriedelCrafts
addition of ethylene oxide to benzene.
This is fairly efficient despite some
addition of ethylene oxide to the product
to give a small amount of polyethoxylated
derivatives.
The major disadvantage of this route is
the safety issue relating to handling of
ethylene oxide and benzene. Both
reagents can be handled safely, but the
engineering required to do so adds to the
process costs.

PERFUME INGREDIENTS
DERIVED FROM TOLUENE
Air oxidation of toluene gives predominantly benzoic acid.
This is used in perfumery for the preparation of benzoate
esters, benzophenone and various other compounds, but
this use is dwarfed by the other industrial uses of benzoic
acid.
It is used in many different ways, for instance, as
precursor for nylon monomers. Crude benzoic acid
contains a small amount of benzaldehyde and this is
easily extracted from it.
In view of the huge volume of benzoic acid produced, the
volume of benzaldehyde recovered from it makes a
substantial contribution to that used by the perfumery
industry.

PERFUME INGREDIENTS
DERIVED FROM PHENOL

Phenol is a material of major commercial importance. One of its earliest uses was as
a disinfectant (carbolic acid).
Earlier in the twentieth century, it became important as a feedstock for resins such as
Bakelite, and in the latter part of the century, it also became very important as a
precursor for caprolactone and caprolactam and hence polyester and polyamide
manufacture.
The two major methods for phenol production nowadays are by catalytic oxidation of
benzoic acid and catalytic decomposition of cumene hydroperoxide.
Diphenyl oxide, prepared from phenol, is important in rose and other floral
fragrances.

PERFUME INGREDIENTS DERIVED

FROM NAPHTHALENE
Acetylation of naphthalene gives methyl naphthyl ketone
and sulfonation, followed by alkaline fusion, gives
naphthol.
The methyl and ethyl ethers of naphthol are prepared
from naphthol by reaction with the corresponding alkyl
sulfate under basic conditions. These ethers are usually
known by the shorter names of yara and nerolin,
respectively.
Yara, nerolin and methyl naphthyl ketone possess floral
odours and are moderately important perfume
ingredients. The name nerolin is derived from neroli, a
synonym for orange blossom oil.

PERFUME INGREDIENTS DERIVED

FROM ALIPHATIC MATERIALS

A large number of aliphatic

fragrance ingredients are
used, but few in significant
tonnage. This is largely
because the materials of
use are mostly aldehydes,
nitriles and lactones, the
majority of which have very
intense odours which limit
the amount that can be
incorporated in a fragrance.
A number of volatile esters
are also used to give fruity
top-notes but, again, these
are not used at high levels.
Some typical examples,
with their odour
descriptions, are shown in
Figure 4.73.

The majority of ingredients of this class can be

prepared by straightforward synthetic reactions and
functional group interconversions, starting from both
natural and petrochemical precursors.

PERFUME INGREDIENTS DERIVED

FROMCYCLOPENTANONE

The chemistry of synthetic jasmine materials was given an

enormous boost in the 1930s when Nylon 66 was launched as a
product.
Nylon 66 is a polyamide prepared using adipoyl chloride and
hexamethylenetetramine as monomers. The 66 in the name refers
to the fact that there are six carbons in each type of unit, which lies
between the amide links in the polymer chain.
Thus, adipic acid is the key feedstock for Nylon 66 and the
introduction of the latter meant that the former became a basic
chemical commodity.
Pyrolysis of the calcium or barium salt of adipic acid produces
cyclopentanone, and so the availability of large quantities of the acid
meant that the ketone could also be prepared at low cost.

PERFUME INGREDIENTS DERIVED

FROM DICYCLOPENTADIENE
Dicyclopentadiene is a feedstock for both the fragrance
and polymer industries.
It forms spontaneously from cyclopentadiene by a
DielsAlder reaction and a retro-DielsAlder reaction
can be used to regenerate cyclopentadiene from it.
A number of minor fragrance ingredients are produced
by Diels Alder reaction of the monomer with a variety
of activated olefins in which the activating group, X, is
usually an aldehyde, ketone, ester or nitrile.
However, the main fragrance uses stem from the dimer.

MANUFACTURING PROCESS

Collection
Before the manufacturing process
begins, the initial ingredients must be
brought to the manufacturing center.
Plant substances are harvested from
around the world, often hand-picked for
their fragrance.
Animal products are obtained by
extracting the fatty substances directly
from the animal.

Extraction

Oils are extracted

from plant
substances by
several methods:
1. Steam distillation
2. Solvent extraction
3. Enfleurage
4. Maceration
5. Expression

Aging

Blending

Fine perfume is often

aged for several months
or even years after it is
blended. Following this, a
"nose" will once again test
the perfume to ensure
that the correct scent has
been achieved.

Once the perfume oils are

collected, they are ready
to be blended together
according to a formula
determined by a master
in the field, known as a
"nose."

Perfumed
Products
Fine Fragrance
(Happy, Chanel No. 5, etc)
Air Care
(Candles, Electricals, etc)
Fabric Care
(Detergents, Conditioners,
etc)
Personal Care
(Shampoos, AP/DEOs, etc)
Personal Wash
(Bar Soaps, Liquid Body or
Hand Wash, etc)
Home Care
(Dish Wash, All Purpose
Cleaners, etc)

Chemistry of
FLAVOURS

Flavour
o sensory impression of a food or
other substance, and is determined mainly
by the chemical senses of taste and smell.
o involves the combination of the four basic
stimuli with the concurrent odor sensations.
encompassing both aroma and taste
provides the defining characteristic of how
we experience food.

Taste
Flavor has long been an
enigma to scientists:
Aristotle described two
categories of taste,
sweet and bitter. Today
we recognize five basic
tastes in food:
Sweetness
Saltiness
Sourness
Bitterness
umami (savory).

Although the essential oils used in

flavouring are the same grade and source
as those used for perfumes fruit flavors are
handled in a somewhat different manner.
Because of the large percentage of water in
most common fruits (75% in the banana to
90% in the strawberry) and the presence of
considerable amounts of sugar other easily
fermented materials.

Flavorants
Foods may contain more than a thousand
chemical compounds that contribute to their
flavour. Many of these naturally occurring
compounds may be too unstable to be used
in commercial flavourings where they may
need to be stored for some time before
being used. For this reason, 'copies' of the
natural flavour are often developed.
Flavorant is defined as a substance that
gives another substance flavor, altering the
characteristics of the solute, causing it to
become sweet, sour, tangy, etc.
Flavourings are used in food products at
very low concentrations. They are normally
made from a mixture of substances which
provide a flavouring of suitable strength that
can be stored and then used in the food
production process.

 A food's flavor, therefore, can be easily altered by changing

its smell while keeping its taste similar. Nowhere is this
better exemplified than in artificially flavored jellies, soft
drinks and candies, which, while made of bases with a
similar taste, have dramatically different flavors due to the
use of different scents or fragrances.

Due to the high cost or unavailability of natural flavor extracts, most

commercial flavorants are nature-identical, which means that they are
the chemical equivalent of natural flavors but chemically synthesized
rather than being extracted from the source materials.
Identification of nature-identical flavorants are done using
technology such as headspace techniques.

Flavorings are focused on altering the flavors of

natural food product such as meats and vegetables,
or creating flavor for food products that do not have
the desired flavors such as candies and other
snacks.

Flavourings
may
contain ...

Flavouring Substances
are chemically defined substances with flavouring properties.

Natural Flavoring Substances

Nature-identical Flavoring Substances
Artificial Flavoring Substances

Flavouring Preparations
- are natural complexes used because of their flavouring properties. They
contain flavouring constituents and they are obtained by appropriate physical,
microbiological or enzymatic processes from foodstuffs or other material of
vegetable or animal origin, either in the raw state or after processing for human
consumption by traditional food-preparation processes (including drying,
torrefaction and fermentation).

Process Flavourings
-means products which are obtained according to good manufacturing
practices by heating a mixture of ingredients to a temperature not exceeding 180
C for a period not exceeding 15 min , the ingredients themselves not
necessarily having flavouring properties, and at least one of which contains
nitrogen (amino) and another is a reducing sugar.

Smoke Flavourings
-means smoke extracts used in traditional foodstuff smoking processes
Primary smoke condensate
Primary tar fraction
Primary products
Derived smoke flavourings

Flavouring Adjuvants.
- are foodstuffs, food additives, other food ingredients or processing aids
which are necessary to ensure the safety and quality of flavourings and to
facilitate the production, storage and intended use of flavourings.
Flavouring adjuvants may also include flavour modifiers.

 Most artificial flavors are

specific and often complex
mixtures of singular naturally
occurring flavor compounds
combined together to either
imitate or enhance a natural
flavor.
These mixtures are formulated
by flavorists to give a food
product a unique flavor and to
maintain flavor consistency
between different product
batches or after recipe changes.
Many flavorants consist
of esters, which are often
described as being "sweet" or
"fruity".

Chemical

Odor

Diacetyl

Buttery

Isoamyl acetate

Banana

Benzaldehyde

Bitter almond

Cinnamaldehyde

Cinnamon

Ethyl propionate

Fruity

Methyl anthranilate

Grape

Limonene

Orange

Ethyl decadienoate

Pear

Allyl hexanoate

Pineapple

Ethyl maltol

Sugar, Cotton candy

Ethylvanillin

Vanilla

Methyl salicylate

Wintergreen

 The compounds used to produce artificial flavors are almost identical to

those that occur naturally. It has been suggested that artificial flavors may
be safer to consume than natural flavors due to the standards of purity
and mixture consistency that are enforced either by the company or by
law.
Natural flavors in contrast may contain impurities from their sources
while artificial flavors are typically more pure and are required to undergo
more testing before being sold for consumption.
Flavors from food products are usually the result of a combination of
natural flavors, which set up the basic smell profile of a food product
while artificial flavors modify the smell to accent it

Flavor Enhancer
Glutamic acid salts
This amino acid'ssodiumsalt,monosodium glutamate(MSG),
is one of the most commonly used flavor enhancers in food
processing. Mono and diglutamate salts are also commonly used.
Glycinesalts
Simple amino acid salts typically combined with glutamic acid
as flavor enhancers.
Guanylic acid salts
Nucleotide salts typically combined with glutamic acid as
flavor enhancers.
Inosinic acidsalts
Nucleotide salts created from the breakdown of AMP. Due to
high costs of production, typically combined with glutamic acid
as flavor enhancers.

 5'-ribonucleotidesalts
Nucleotide salts typically combined with other
amino acids and nucleotide salts as flavor enhancers.

Acetic acid
Gives vinegar its sour taste and distinctive
smell
Ascorbic acid
Found in oranges and green peppers and gives a
crisp, slightly sour taste. Better known asvitamin C.

Citric acid
Found in citrus fruits and
gives them their sour taste
Fumaric acid
Not found in fruits, used as a substitute for citric and tartaric acid

Lactic acid
Found in various milk orfermented
productsand give them a rich tartness

Malic acid
Found in apples and gives them
their sour/tart taste
Phosphoric acid
Used in all cola drinks to give
an acid taste

Tartaric acid
Found in grapes and wines and
gives them a tart taste

Natural Flavoring
Substances

Flavoring substances
obtained from plant or
animal raw materials,
by physical,
microbiological or
enzymatic processes.
They can be either
used in their natural
state or processed for
human consumption,
but cannot contain any
nature-identical or
artificial flavoring
substances.

Nature-Identical
Flavoring
Substances
Flavoring
substances that are
obtained by synthesis
or isolated through
chemical processes,
which are chemically
and organoleptically
identical to flavoring
substances naturally
present in products
intended for human
consumption. They
cannot contain any
artificial flavoring
substances.

Artificial Flavoring
Substances
Flavoring substances
not identified in a natural
product intended for
human consumption,
whether or not the
product is processed.
These are typically
produced by fractional
distillation and additional
chemical manipulation of
naturally sourced
chemicals, crude
oil or coal tar. Although
they are chemically
different, in sensory
characteristics are the
same as natural ones.

1. Primary smoke condensate shall refer to the purified

water-based part of condensed smoke and shall fall
within the definition of smoke flavourings.
2. Primary tar fraction shall refer to the purified fraction of
the water-insoluble high-density tar phase of condensed
smoke and shall fall within the definition of smoke
flavourings.
3. Primary products shall refer to primary smoke
condensates and primary tar fractions.
4. Derived smoke flavourings shall refer to flavourings
produced as a result of the further processing of primary
products and which are used or intended to be used in or
on foods in order to impart smoke flavour to those foods.