CHEMISTRY OF FLAVORS AND FRAGRANCES

Objectives:

 Define what fragrances are

 Define what

Introduction

Fragrance and flavor materials are used in a wide variety of products, such as soaps, cosmetics,
toiletries, detergents, alcoholic and non-alcoholic beverages, ice cream, confectioneries, baked
goods, convenience foods, tobacco products, and pharmaceutical preparations.

Since early antiquity, spices and resins from animal and plant sources have been used
extensively for perfumery and flavor purposes, and to a lesser extent for their observed or
presumed preservative properties. Fragrance and flavor materials vary from highly complex
mixtures to single chemicals. Their history began when people discovered that components
characteristic of the aroma of natural products could be enriched by simple methods. Recipes
for extraction with olive oil and for distillation have survived from pre-Christian times to this
day (Surburg & Panten, 2006).

Although distillation techniques were improved, particularly in the 9th century A.D. by the
Arabs, the production and application of these concoctions remained essentially unchanged for
centuries. Systematic development began in the 13th century, when pharmacies started to
prepare so-called remedy oils and later recorded the properties and physiological effects of
these oils in pharmacopoeias. Many essential oils currently used by perfumers and flavorists
were originally prepared by distillation in pharmacies in the 16th and 17th centuries.

Another important step in the history of natural fragrance materials occurred in the first half of
the 19th century, when the production of essential oils was industrialized due to the increased
demand for these oils as perfume and flavor ingredients. The first synthetic “aroma oils” were
introduced between 1845 and 1850. These consisted of lower molecular mass fatty acid esters
of several alcohols and were synthesized by the chemical industry for their fruity odor. Methyl
salicylate followed in 1859 as “artificial wintergreen oil” and benzaldehyde in 1870 as
“artificial bitter almond oil.” With the industrial synthesis of vanillin (1874) and coumarin
(1878) by Haarmann & Reimer (Holzminden, Federal Republic of Germany), a new branch of
the chemical industry was founded.

Fragrance and flavor substances are comparatively strong-smelling organic compounds with
characteristic, usually pleasant odors. They are, therefore, used in perfumes and perfumed
products, as well as for the flavoring of foods and beverages. Whether a particular product is
called a fragrance or a flavor substance depends on whether it is used as a perfume or a flavor.
Fragrances and flavors are, like taste substances, chemical messengers, and their receptors
being the olfactory cells in the nose.

Fragrances

Fragrances are collectively known as the manufacture of perfume, cologne, and toilet water.
According to Austin (1994), only occasionally was a new and original odor developed, such as
Old Spice, which immediately won spontaneous and favorable response from consumers. Not
many people realize how complex the creation of an acceptable fragrance has become; it
requires professional knowledge, skill, and experience, coupled with specialization in synthetic
chemistry’s technical problems, followed by consumer panel testing.

Fragrances make a major contribution to the cosmetic industry, second only to the amount used
in soaps and detergent. They are used industrially in masking, neutralizing, and altering the
odor of various products, as well as in creating a distinctive aroma for normally odorless
objects.

Perfume Industry

Perfume takes its name from the Latin word “perfumare” which means “to fill with smoke”,
since in its original form it was incense burned in Egyptian temples. It is defined as any mixture
of pleasantly odorous substances incorporated in a suitable vehicle. Formerly, practically all
the products used in perfumery were of natural origin. Even when human first started
synthesizing materials for use in this field, they endeavored to duplicate the finest in nature.
The constituents of perfumes are: the vehicle or solvent, the fixative, and the odoriferous
elements.

Vehicles. The modern solvent for blending and holding perfume materials is highly refined
ethyl alcohol mixed with more or less water according to the solubility of the oils employed.
In its volatile nature, it helps to project the scent it carries, fairly inert to the solutes, and is not
too irritating to human skin.
Fixatives. These are substances of lower volatility than the perfume oils, which retard and even
up the rate of evaporation of the various odorous constituents. The types of fixative considered
are animal secretions, resinous products, essential oils, and synthetic chemicals. Any of these
fixatives may or may not contribute to the odor of the finished product but, if they do, they
must blend with and complement the main fragrance.

Odorous Substances. Most odorous substances used in perfumery come under three headings:
(1) essential oils, (2) isolates, and (3) synthetic or semisynthetic chemicals. Essential oils may
be defined as volatile, odoriferous oils of vegetable origin. Isolates are pure chemical
compounds whose source is an essential oil or other natural perfume material. Synthetic or
semisynthetic chemicals are chemically synthesized from an isolate or other natural starting
materials that account for more than 50% of the fragrances used in perfumes.

Perfumes are a blend of different levels of scent, also called “notes”. When you spray a
fragrance on your skin, it moves through these notes in the following order:

 Top notes are what you smell first. They are also what disappears first, usually within
10 to 15 minutes.
 Middle notes appear as the top notes die off. These are the fragrance’s core,
determining which family the perfume belongs to — for example, oriental, woody,
fresh, or floral.
 Base notes accentuate and fix the fragrance’s middle notes, also known as its theme.
They comprise the fragrance’s foundation, making the scent last up to 4 or 5 hours on
your skin.

Essential Oils

“Essential” does not mean “most necessary” but rather the concentrated characteristics or
quintessence of a natural flavor or fragrance raw material. Essential oils are, in the main,
insoluble in water and soluble in organic solvents, although enough of the oil may dissolve in
water to give intense odor to the solution, as in the case of rose water and orange flower water.

The compounds occurring in essential oils may be classified as follows:

Esters. Mainly of benzoic, acetic, salicylic, and cinnamic acids.

Alcohols. Linalool, geraniol, citronellol, terpinol, menthol, borneol.

Aldehydes. Citral, citronellol, benzaldehyde, cinnamaldehyde, cuminic aldehyde, vanillin

Acids. Benzoic, cinnamic, myristic, isovaleric in the free state

Phenols. Eugenol, thymol, carvacrol

Ketones. Carvone, menthone, pulegone, irone, fenchone, etc.

Esters. Cineole, internal ether (eucalyptole), anethole, safrole

Lactones. Coumarin

Terpenes. Camphene, pinene, limonene, phellandrene, cedrene

Hydrocarbons. Cymene, styrene (phenylethylene)

Any or all parts of the plant may contain oil. Essesntial oils are found in buds, flowers, leaves,
bark, stems, fruits, seeds, wood, roots, and rhizomes and in some trees in oleoresinous exudates.

Volatile oils may be recovered from plants by a variety of methods. (1) expression, (2)
distillation, (3) extraction with volatile solvents, (4) enfleurage, and (5) maceration.

Expression by a machine can yield an oil almost identical to the hand- pressed product, and is
the method used commercially. Here, let’s take for an example a lemon. The fruit is halved,
and the peel trimmed and soaked in water for several hours. Each peel is pressed against a
sponge, and the oil is ejected into the sponge, which is periodically squeezed dry.

Distillation, usually with steam. Flowers and grasses are normally charged into the still without
preparation. Leaves and succulent roots and twigs are cut into small pieces. Dried materials are
powdered. Woods and tough roots are sawed into small pieces or mechanically chipped. Seeds
and nuts are fed through crushing rolls spaced so as to crack them.

Extraction with volatile solvents. The most important factor in the success of this practice is
the selection of solvent. The solvent must be selective (quickly and completely dissolve the
odoriferous components, but have only a minimum of inert matter), have a low boiling point,
be chemically inert to the oil, evaporate completely without leaving any odorous residue, and
be low- priced and, if possible, nonflammable.

Enfleurage process is a cold- fat extraction process used on a few types of delicate flowers
which yield with no direct oil at all on distillation.
FLAVORING INDUSTRY

There are only four basic flavors which the nerve endings in the taste buds on the tongue can
detect: sweet, sour, salty, and bitter. The popular conception of flavor, however, involves the
combination of these four basic stimuli with concurrent odor sensations. Apple, for instance,
tastes merely sour, with a trace of bitterness from the tannins present. The main concept
received of an apple is due to the odor of acetaldehyde, amyl formate, amyl acetate, and the
other esters present in the volatile portion. The principles of perfume blending also hold good
for flavor manufacturing. Many essential oils find application in the flavor industry, the more
common being spice oils, citrus oils, peppermint, and spearmint.

Natural Fruit Concentrates

Although the essential oils used in flavoring 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 (from 75% in the banana to 90% in the strawberry)
and the presence of considerable amounts of sugar and other easily fermented materials, special
processes must frequently be employed, such as distillation and extraction of the fruit,
extraction of the juice, and concentration of the juice. Examples for this natural fruit
concentrates are vanilla (from vanilla bean) and chocolate and cocoa (from cacao bean).

References:

Austin, G. (1984). Shreve’s chemical process industries. McGraw- Hill Book Company.

Dorland and Rogers, The Fragrance and Flavor Industry, Dorland, Mendham, N.J., 1977.

Hornstein and Teranishi, The Chemistry of Flavor, Chem. Eng. News 45 (32) 93 (1967).

Mitchell et. al., “Importance of Odor as a Nonfunctional Component,” Odor Symposium, New
York Academy of Sciences, November 7-9, 1963.