ORGANIC CHEMISTRY

ASSIGNMENT 1:
APPLICATION OF ORGANIC
REACTION
IN INDUSTRY (PERFUME)

NAME: MUHAMMAD FAKHRUSSYAKIRIN BIN ROSLI

ID NUMBER: 55220115350
GROUP: A
LECTURER: DR. NORZAHIR BIN SAPAWE

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 CONTENT

INTRODUCTION………………………………………………………………….3

PROCESS…………………………………………………………………………..5

DISCUSSION………………………………………………………………………8

CONCLUSION…………………………………………………………………….9

APPENDICES…………………………………………………………………….10

REFERENCES……………………………………………………………………12

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 1. Introduction

1.1 History

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 characteristics 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.
Although distillation techniques were improved, particularly in the 90th 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 oil in
pharmacopoeias. Many essential oils currently used by perfumers and flavorists were originally
prepared by distillation in pharmacies in the 16th and 17th centuries.
Around 1850, single organic compounds were also used for the same purposes. This development
resulted from the isolation of cinnamaldehyde from cinnamon oil in 1834, and the isolation of
benzaldehyde from bitter almond oil in 1837. 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.
The number of synthetically produced fragrance and flavor chemicals has since expanded
continually as a result of the systematic investigation of essential oils and fragrance complexes for
odoriferous compounds. Initially, only major components were isolated from natural products and
their structure was then elucidated and processes were developed for their isolation or synthesis.
With the development of modern analytical techniques, however, it became possible to isolate and
identify characteristics fragrance and flavor substances that occur in the natural products in only
trace amounts. The isolation and structure elucidation of these components requires the use of
sophisticated chromatographic and spectroscopic techniques. Interesting products can then be
synthesized.

1.2 Definition

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

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 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, their receptors being the olfactory cells in the nose.

1.3 Natural, Nature-identical, and Artificial Products

Natural compounds are obtained directly from natural sources by physical, enzymatic or microbial
procedures. Nature-identical compounds are produced synthetically, but are chemically identical to
their natural counterparts. Artificial flavor substances are compounds that have not yet been
identified in plant or animal for human consumption. Alcohols, aldehydes, ketones, esters, and
lactones are classes of compounds that are represented most frequently in natural and artificial
fragrances.
Nature-identical aroma substances are, with very few exceptions, the only synthetic compounds
used in flavors besides natural products. The primary functions of the olfactory and taste receptors,
as well as their evolutionary development may explain why artificial flavor substances are far less
important. Considerable proportions of compound used in fragrances are those identified as
components of natural products such as constituents of essential oils or resins. The fragrance
characteristics of artificial compound nearly always mimic those of natural products.

Aldehyde Ketone Ester Alcohol Lactones

1.4 Sensory Properties and Structure

Similarity between odors arises because dissimilar substances or mixtures of compounds may
interact with receptors to create similar sensory impressions in the sensory centers of the brain. The
group of musk fragrances such as comprising macrocyclic ketones and esters as well as aromatic
nitro compounds and polycylic aromatics are compounds with similar odors but totally different
structures. Small change of structure (e.g. the introduction of one or more double bonds in aliphatic
alcohols or aldehydes) may, however, alter a sensory, impression or intensify an odor by several
orders of magnitude. Increasing knowledge of the structure and functioning of olfactory receptors
provides a better scientific basis for the correlation of odor and structure in fragrance and flavor
substances, and facilitates the more accurate prediction of the odors of still unknown compounds.

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 2. Processes

2.1 Nature of the raw materials

The basic odoriferous components of perfumes number 4000-6000, of which about 100 are frequently
used. Examples include benzyl acetate, cedar oil, geraniol, lavender oil and vanillin. There are two groups
of odoriferous raw materials. Natural (which are plant and animal extracts) and synthetic (generally
derived from crude oil or turpentine). Originally nearly all products used in perfumery were of natural
origin. Today, many modern perfumes are a blend of synthetic and natural substances.

The constituents of a typical perfume are shown below:

Metallic compounds Manganese dioxide, chromic acid

Solvents Usually highly refined ethyl alcohol mixed with varying amount
of water.

i) Alkanes: dimethyl butane, petyroleum ether

ii) Aromatics: benzene, toluene
iii) Esters: benzyl benzoate, benzyl acetate

Fixatives These are substances which have lower volatility than the other
components including:

i) animal fixatives such as civet, musk, ambergris

ii) oily plant fixatives such as castor oil
iii) resinous plant fixatives such as terpenes and labdanum
iv) synthetic fixatives such as glyceryl diacetate and coumarin
v) essential oil fixatives such as clary, sage and sandalwood

Odoriferous elements Essential oils come from plants such as rose oil, orange flower, clove
oil.
Isolates are chemicals isolated from essential oils such as eugenol
from clove oil.
Synthetic and semi-synthetics.

2.2 Manufacturing processes

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The first stage in the manufacturing of perfumes involves the production of the odoriferous component.
The actual perfume is manufactured, or compounded by blending processes which involve the batch
weighing of the ingredients and mixing with heating and cooling, followed by filtering.

Production of natural odoriferous compounds

The main processes used to produce natural odoriferous compound are expression, distillation and
extraction, using enfleurage, maceration or volatile solvents.

Juice is squeezed from fruit by one of two methods:

i) The ecuelle process in which the fruit is rolled in a hollow vessel with spiked walls
ii) The machine process in which the fruit is spiked and squeezed. Once collected, the juice is
clarified.

Distillation is usually performed with steam. Stills of copper, tin-lined copper or stainless steel are used
with condensers of various types. A separator divides the oily and aqueous layers. The aqueous layer of
the distillate, which may contain valuable constituents, is usually pumped back into the still.

Enfleurage is cold fat extraction, used to obtain a few delicate flower perfumes such as jasmine and
violet. The fat used for this process is a highly purified mix of tallow and lard with gum benzoin as the
preservative. This method is no longer used on a commercial basis.

Extraction with volatile solvents is the most common process used today to obtain natural odoriferous
components of perfumes. The solvent usually employed is highly purified petroleum ether. Benzene was
often used in the past. The extraction equipment consists of stills for fractionating the solvent, drums for
extracting essential oils from the flowers and stills for concentrating the flower-oil solutions.

Production of synthetic or semi-synthetic odoriferous compounds

Constituents which are chemically synthesized from natural materials are classified as semi-synthetics.
Those synthesized from man-made materials are synthetics. The main types of reactions utilized for the
manufacture of synthetic odoriferous compounds:

Oxidation This is carried out usually with manganese dioxide, chromic acid, oxygen
such as manufacture of vanillin using nitrobenzene as the oxidizing agent.

Condensation Used in the manufacture of coumarin, ionone and cinnamic aldehyde.

Hydrogenation Hydrogenation is the principal reaction used in large scale production of

fragrances.

Alkylation Used for example in the synthesis of phenylethyl alcohol from benzene and
ethylene oxide.

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Esterification Used for example in the synthesis of benzyl benzoate, benzyl acetate, amyl
salicylate and methyl salicylate.

Blending
The compounding of perfumes to produce concentrates in bulk is simple but must be performed with
great precision. Generally, solids are added to the solvent and dissolved using high speed stirring with or
without heat. The mixture is cooled and the remaining ingredients are added. Firstly, the more volatile
compounds are added, followed by the resins, the more stable aromatic and finally any remaining
ingredients. The solution is filtered to remove any solids.

2.3 Finishing products

The finished product from the perfume manufacturing process may either be sales unit that is small
bottles of perfume, aerosols, solid pencil, or small drums, typically 10 kg in size of perfume concentrate
for use in the manufacture of other products, in particular toiletries. Handling and storage practices
depend on the specific nature of the final products. The products are likely to be stored on pallets or in
boxes in warehouses until they are transferred to a loading area by fork-lift truck and dispatched by lorry.

2.4 Ancillary activities

Most perfume manufacturers have a quality control testing laboratory on site and some may also have
product development laboratories. A wide range of organic and inorganic laboratory reagents are used in
these activities but in very small quantities. However, it is possible that larger volumes of laboratory
reagents may be kept in stock on site.

The manufacture of perfumes requires the use of very pure water in the formulations. Therefore, mains
water is usually de-ionised, sterilized and filtered on site. Sodium hydroxide and hydrochloric acid are
usually used in the ion exchange process for the regeneration of ion exchange resin.

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 3. Discussion

The odor of single chemical compound is extremely difficult to describe unequivocally. The odors of
complex mixtures are often impossible to describe unless one of the components is so characteristic that it
largely determines the odor or flavor of the composition. Although an objective classification is not
possible, an odor can be described by adjectives such as flowery, fruity, woody, or hay-like which relate
to natural or other known products with similar odors.

Simple esters tend to have pleasant odor. In most cases the characteristic flavors and fragrances of flowers
and fruits are due to the compounds with the ester functional group. An exception is the essential oils.
Although the odors and flavors can be due to single esters, more often the aroma is due to a complex
mixture in which single ester predominates.

Ester

Perfumes are products of the “esterification” reaction occurring between alcohols and acids. Water is
separated as a second product. The reverse reaction is called “hydrolysis”.

Esters have small molecular weight and very nice odor. The higher the molecular weight, the weaker the
odors they carry are. Unsaturated esters have stronger odor than the saturated ones. Esters are used in the
fragrance and flavoring industries. They also have implication as fixatives and carried solvents.

Benzyl Acetate is one of thousands of esters that can be used for perfume ingredients. It is an extremely
significant compound because it provides basic odor that can be found in many of the perfumes and other
cosmetic products. Benzyl acetate is a primary constituent of the essential oils from the flowers jasmine
and ylang-ylang. Therefore, it is widely used in perfumery and cosmetics for its aroma and in flavorings

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to stimulate apple, banana, strawberry, and pear flavors. In a process not industrially conducted, benzyl
acetate is produced by reaction of toluene, acetic acid, and oxygen in the presence of a catalyst.

4. Conclusion

Perfume is a combination of many aromatic compounds and solvents with specific essential oils and
fixatives. Overall, this combination produces a nice smell in environment and human body. Keeping
perfumes in a protected place, away from heat and light, can guarantee a longer shelf life.

Perfume making is a complex process of mixing all necessary ingredients in specific proportions to get
the desired effect. Plants, flowers, leaves, and bark are important natural sources of aromatic compounds
and different essential oils. Different parts of different plants give different aromas. Animals are also
important sources of special aromas like odorous sacs of the civets, musk sacs from Asian musk deer,
honeycomb of the honeybee, and others. Presently most of the perfumes contain synthetic aromatic
compounds like those from petroleum distillates, coal tar, organic feedstock, or pine resins. Synthetic
compounds are beneficial and prove to be good alternate sources for compounds that are difficult to
obtain from natural sources.

Ester is a basic compound that used in perfume making. An ester is the product of an acid-catalysed
condensation between an alcohol and a carboxylic acid. Esters have identification aromas (like the
fragrant smell and odor of fruit) and are used in perfumes. Esters are less water soluble than the
carboxylic acid they were formed from and appear as an oily substance on water. Before being cooled
however some of the ester would have been a vapour, so the wet paper towel would help to prevent a loss
of the product.

Esters are the main thing for sniff fruits and flowers smell. The scent of pineapple, for example, is largely
due to the molecules alkyl hexanoate, butyl butyrate, ethyl butyrate, and pentyl hexanoate. Esters that
make up perfumes and sweet fruity flavorings start out with bad smelling organic acids, like butyric acid
(which gives rancid butter its odor), acetic acid (which give vinegar its sharp smell), or hexanoic acid
(which give the smell of goats in a barnyard).

Another class of chemical used in perfumes are aldehydes. Cinnamaldehyde gives cinnamon its aroma.
Furfural is an aldehyde that smells like almonds. Benzaldehyde is another aldehyde in almond scent.
Vanillin is an aldehyde that gives another popular flavoring its aroma. A perfume typically has a hundred
or so different chemicals in it, and some have several hundred.

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 5. Appendices

TABLE 1

n-propyl acetate Pear Isobutyl propanoate Rum

Isopentyl acetate Banana n-octyl acetate Orange
Methyl salicylate Wintergreen Methyl anthranilate Grape
Benzyl acetate Peach Isobutyl propanoate Floral
Ethyl propanoate Fruity Propyl propanoate Pineapple
Butyl benzoate Balsamic Methyl benzoate Prune
Ethyl benzoate Fruit Geranyl acetate Rose

TABLE 2

Pure Compound % Essential Oils %

Ally caproate 5 Oil of sweet birch 1
Isoamyl acetate 3 Oil of spruce 2
Isoamyl isovalerate 3 Balsam Peru 4
Ethyl acetate 15 Volatile mustard oil 1
Ethyl butyrate 22 Oil cognac 5
Terpinyl propionate 3 Conc. Orange oil 4
Ethyl crotonate 5 Distilled oil of lime 2
Caproic acid 8 19
Butyric acid 12
Acetic acid 5
81

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Figure B: Oils are extracted from plant substances by steam
distillation, solvent extraction, enfluerage, maceration
or expression.

Figure C: It is the ratio of alcohol to scent

that determines perfume,
eau de toilette and cologne.

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 6. References

Ash M and Ash I. A formulary of cosmetic preparations. Chemical Publishing Company, New York,
1977
Maller P M and Lamparsky D. Perfumes, art, science and technology. Elseiver, 1991.

https://en.wikipedia.org/wiki/Fragrance_extraction

https://en.wikipedia.org/wiki/Perfume

http://www.bbc.co.uk/schools/gcsebitesize/science/ocr_gateway/carbon_chemistry/smellsrev1.shtml

http://www.chemistryislife.com/the-chemistry-of-perfume

http://www.madehow.com/Volume-2/Perfume.html

http://www.sciencebuddies.org/science-fair-
projects/project_ideas/Chem_p083.shtml?from=Blog#makeityourown

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