chapter gY
The Perfume Induslry 485
Fpagrallccs,
aDd Food
THE PERFUME' INDUSTRY
^tEilfliI;
The manufacture of cerfume, cologne, and toilet water, collectively known as the fragrances,
has undergone drastic changes in the past quarter century, prior to which perfumers were
rrsually trained through apprenticeships in laboratories until, working with traditional mate-
rials in well-defined patterns, they achieved skill in mixing and blending. Only occasionally
was a new and original odor developed, such as old spice, which immediately won sponta-
neous 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 chemibtry's technical problems, followed
by consumer panel testing. This change has resulted from a number of factors, for example:
(I) increase in the number of available raw-material ingredients, both natural and synthetic;
(2) a variety of new types of products requiring fragrances; (3)'innovations in packaging,
especially aerosol sprays, virtually nonexistent before 1g50, and other new forms of dispensing
such as perfume powders, cream sachets, gels, lotions, and sticks;(4) broadened channels and
methods of distribution, including door-to-door seiling; and (5) phenomenal growth in.men's
toiletries. These numerous recent develdpments are in contrast to the two main changes which
took place earlier, the introduction of synthetics and improved methods of ot,tainirrjtrue oils,
Perfume takes its iarne from the Latin word perlumara (to fill with smoke), since in its
original form it was incense burned in Egyptian temples. Early incenses were nrerely mix-
tures of finely ground spices held together by,myrrh or storax. The next advance was the
discovery that; if certain spices and flowers were steeped in fat or oil, the fat or oil would
retain a portion of the odoriferous principle. Thus were manufactured the ointments un{
fragrant unguerrts of Biblical fame. Avicenna, the Arabian physician, discovered steanr dis-
tillation of volatile oils. During his search for medical potions, he found that flowers boiled tlr
an alembic with water gave up some of their essence to the distillate. The returning Crusaclers
brought to Europe all the art and skill of the orient in perfumery, as well as informuti6n
relating to sources of gums, oils, and spices. Ren6, perfumer to Catherine de' Medici, invented
many new confections to delight the queenly nose and, in l-ris spare time, was one of the
cleverest and deadliest of the famirus de' Medici poisoners. N,lany of the finest perfumes ure
imported from France. Classical colognes are at least 200 years old, having originated irr
IECT, Bd ed., vol 16, 1982, p.947.
4M
Cologne, Germany; they were probably the first imports into this country. It u'as not ur:til
the I950s that U.S; industry discovered that the sale of perfume odors in an alcohol-diluted
form was profitable.
UsEs d/vD ECaNoLrIc& Fragrance shipments were $1800 million in lg8l, and this was a
large iricrease from the $320 million in I974, The popularity of men's fragrances has, no
doubt, contributed greatly to the increase
Fragrances make a major contribution to the cosmetic industry, second only to the amount
used in soaps and detergents. Fragrances are used industrially in masking, neutraliring, and
altering the odor of various products, as well as in creating a'distinctive aroma for normally
odorless objects. Cashmere shawls manufactured in Scotland are given the Hindu touch by a
trace of patchouli oil applied to them. Aromatics, sometimes referred lo as reodorants, are
added to fabric sizing to disguise the glue or casein smell, leaving the product with a fine
fresh odor. Leather goods and papers are scented delicately to eliminate the raw-material
smell. The odor of kerosene in fly sprays is masked; artificial cedarwood is made by coating
other woods with cedar oil reclaimed in pencil manufacturing. Canneries, rendering plants,
municipal refuse plants, and food processing systems are other areas where reodorants are
used- Paint odor during drying is masked by essential oils and fixatives introduced in small
quantities in the bulk product. Odors are used successfully to increase customer appeal,
though they are not essential to the performqnce of the.products to which they are added,2
A minute amount of bornyl acetate evaporated in an air-conditioning system imparts an out-
door tang to the air.
"ttConstituents
A perfume may be detined as any mixture of pleasantly odc,rous substances incorporated in
a suitable vehicle. Formerly, practically all the products used in perfumery were of natural
origin. Even when humans first started synthesizing materials for use in this field, they
errdeavored to duplicate the finest in nature..Theri has been a marked tendency in'recent
years, however, to rnarket perfumes which have no exact counterpart in the floral kingdom
but which have received wide acceptance. The finest modern perfumes are nerther wholly
synthetic nor completely natural. The best product of the art is a judicious blend of the two
in order to enhance the naturaL perfume, to reduce the price, and to introduce fragrances
into the enchantlng gamut at present available. A product made solely of synthetics tends to
be coarse and unriatural because of the absence of impurities in minute amounts which finish
and round out the bouquet of natural odors; however, such an eventual development is pre-
dicted. The chemist has also succeeded in creating essences of flowers u,hich yield no natural
essence orwhose essence is too expensive or too fugitive to make its extraction profitable. Lily
of the valley, iilac, and violet are examples. The constituents of perfumes are: the vehicle or
solven(, the fixative, and the odoriferous elements.
vEnrcLxs. The modern solvent for blending and holding perfume materials is highly refined
ethyl alcohol mixed with more or less water according to thesolubilities of the oils employed.
This solvent, with its volatile nature, helps to project the sceDt it carries, is fairly inert. to the
zMitchell et al., "lmportance of Odor as a Nonfunctional Component," Odor Symposium,
New York Academy of Sciences, Novembef 7*9, 1903.
',ltf t" rC S
486 Chap.27 Fragrancec, trlavo?a, and food Addlttvce The per!tume Indu.tty 487

irritating to the human skin, The slight natural odor of the alcohol is
solutes, and is not too
removed by deodorizing, or "prefixation," of the alcohol. This is accomplished by adding a
small amount of gum benzoin or othir resinous ftxatives to the alcohol and allowing it to
mature for a *eek o. two. The result is an almost odorless albhol, the natural rawness having
FrxATrvES In an ordinary solution of perfume substances in alcohol, the more volatile mate-
rials evaporate first, and the odor of the perfume consists of a series of irnpressions r.atherthan
the desiied ensemble. To obviate this difficulty, a ffxative is added. Fixatives may be defined
as substanqes 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 arplanimal
,""iitiorr., 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 co,,rplement the main fragrance.
Anirwl Firotiaes. Of all animal products, castor, or castoreun't, a brownish orange exu-
date of the perineal glands of the beaver, is employed in the greatest quantity. Among the
odoriferous components of the volatile oil of castor are benzyl alcohol. acetophenone, l-bor-
neol, an<i castorin (a volatile resinous component of unknown structure)'
Cioet is the soft, fatty secretion of the perineal glands of civet cats, which are indigenous
to many countries, and was developed in Ethiopia. The s'ecretions are collected about every
Recinous Fitatioea Resinous ffxatives are normal or pat'hological exudates from certain
plants, which are more important historically tharr commercially.-These are hard resins,
e.g.,
benzoin and gunrs; softer resins, e.g., myrrh and labdanum; balsams, moderately soft, e.;.,
Peru balsam, tolu balsam, copiaba, and storax; oleoresins, oily materials, e.g., terpenes;
extracts from resins, less viscous, e.g., ambrein. All these substances, when being pr"p..Ld fo.
oerfume compounding, are dissolved and aged by methods passed down by word of mouth.
If solution is brought about in the cold, the mixture istalled a tincture.If heat is required to
give solution, the mixture is an infusion Alcohol is the solvent, sometimes aided by benzyl
benzoate or diethyl phthalate. The most important of the soft gums is Labdanum. The Ieaves
of a plant growing in the Mediterranean area exude this sticlly substance. An extract from
thisgum has an-odor suggestive of ambergri's and is marked as ambrein, having extremely
good fixative value. Of the harder plant resins used in perfumes, benzoin is the most impor-
tant. The history of chemistry was influenced by this substance. The early source of benzoin
was Java, where it was called luban iau:i. Through various contractions and linguistic modi-
fications, it became "banjawi," "benjui," "benzoi," "benzoin," and "benlamln." In early
organic chemical history an aeid isolated from this gum became known as benzoic acid, [rom
which compound the names of all benzo compourrds of today are derived.
Essential-Oil Fixatioes, A few essential oils are used for their fixative properties as well
as their odor. The more important of these are clary sage, vetiver, patchouli, orris, and san-
dalwood. These oils have boiling points higher than normal (2S5 to ZSOog;.
'

4 days by spooning,and are packed for export in hollow horns. The crude civet is disagreeable
in ojor because of the skatole present. On dilution and aging, however, the skatole odor dis- Sgnthetic Firathses. Certain high-boiling, comparatively odorless esters are used as ffx-
appears, and the sweet and somewhat floral odor of civetone, a cyclic ketone, appears. atives to replace-some imported animal fixatives. Among them are glyceryl diacetate (25goC),
ethyi phthalate (2950C), and benzyl benzoate (323"C).bther synt-hetics are used as fixatives,
CH.(CH^),
"')co //\-CH" although they have a definite odor of their own that contributes to the ensemble in which
llcH-(cH2\7/ cH3-c{ ,co
jcfi,),,
they are used. A few of these are
Amyl benzoate Musk ketone Heliotropin
Phenethyl phenylacetate Musk ambrette Hydroxycitronellal
Musk is the dried secretion of the preputial glands of the male musk deer, found in the Cinnamic alcohol esters Benzophenone Indole
Himalayas. The odor is due to a cyclic ketone called muslane, which is present to the extent Cinnamic acid esters Vani.llin Skatole
of from Yrto ZVo. Musk, the most useful of the animal fixatives, imparts body and smoothness Acetophenone Coumarin
to a perfilme composition even when diluted so that its own odor is completely effaced. Musk
is used for its own sake in heavy oriental perfumes. oDonous suBsreNCES. Most odorous substances used in perfumery come
under three
Arnbergris .is the least used, but probably best known,. of the animal fixatives. It is a cal- headings: (1) essential oils, (2) isolates, and (B) synthetic or semisynthetic
chemicals.
culus, or secretion, developed by certain whales. Ambergris is obtained by cutting open the
captured whale, or it is obtained from whales stranded on a beach. It is waxy in consistency, Ecsential Oils.8 Essential oils may be defined as volatile, odorilerous oils of
vegetable
softening at about 60oC, and may be white, yellow, brown, black, or variegated like marble. origin (Table 27.1). A distinction should be made, however, between natural
flower,oils
It is composed of 80 to 85% ambrein (triterpenip tricyclic alcohol), resembling cholesterol and obtained by enfleurage or solvent extraction and essential oils recovered
by distillation. Dis-
acting merely as a binder, and 12 to 15% amb'ergris oil, which is the active ingredient. It is tilled oils may lack some component which is not volatile enough o, *ti"t
is lost during
employed as a tincfure, which must be rnatured before it is used. The odor of .the tinctuie is dlstillation. Two notable examples of this are rose oil, in which pni"ryutr,fr
*icohol is lost to
decidedly musty and has great fixative powers. the watery portion of the distillate, and orange flower oil, in which the
distilled oil contains
Masf zibata is the newest animal fixative, derived from glands of the Louisiana muskrat.
It was only during: World War II that musc zibata was commercialized. About 90% of the 3"Essential"
does not mean "most necessary' but rather the concentrated characteristic
or
unsaponiffabie material in muskrat glbnds consists of large, odorless cyclic alcohols, which are quintessence of a natural flavor or fragrance raw material; Internatioital
Standardtzatton of
converted'to ketones, increasing the characteristic musk odor nearly 50 times. It is a replace- Essential oils, committee ISO/TCS4 publishes standards. see cosrnet. perfum.90 (2) g6
ment for, or an addition t6, Asiatic musk. (r975).
i
i
$
*
$
 The Petfutne Indwtry 489
;i:
Table 27.7 Important Essential Oils
bul a very small proportion of methyl anthranilat.:, whereas the extracted flower oil may
Important
Geographical Method Part of Chief contain as much as one-sixth of this constituent.
Name of Oil Sources of Production Plant Used Constituents Essential oiis are, in the main, insoluble in watet and soluble in organic solvents, although
Benzaldehyde enough of the oil may dissolve in water to give an intetrse odor to the solution, as in the caSe
California, Steam Kernels
Almond, bitter 96-98%, HCN of rose water and orange flower rarter. These oils are volatile enough to distill unchanged in
Morocco
2-4% most instances, and are also volatile with steam. They vary from colorless to yellow or brown
Bay West Indies Steam Leaves Eugenoi 50% in color. An essential oil is usually a mixture of comfounds, although oil of wintergreen is
Peel Linalyl acetate
Bergamot Southern Italy Expression almost pure methyl salici,late. The refractive indexes of the oils are high, averaging about
40%, linalool
6Vo I,5. The oils show a wide range of optical activity, rotating in both directions.
Steam Seed Carvone 55%, The compounds occurring in essential oils may be classified as follows:
Caraway Northern EuroPe,
d-limonene
Holland
Steam Leaves and Cinnamic l. Esters, Mainly of benzoic, acetic, salicylic, and cinnamic acids
Cassia (Chinese C\ina
twigs aldehyde 70% 2. A.cohols, l,inalool, geraniol, citronellol, terpinol, menthol, borneol
cinnamon) Cedrene, cedral
Cedarwood North America Steam Red core wood 3. Atilehydes. Citral, citronellol, benzaldehyde, cinnamaldehyde, cuminic aldehyde,
Cinnamon Ceylon Steam Bark Cinnamic
vanillin lr
aldehyde,
eugenol 4, Acids. Benzoic, cinnamic, myristic, isovaleric in the free state h;

Citronella, Java Java, Ceylon Steam Grass Geraniol 65%,

citronellal
5. Phenols. Eugenol, thymol, carvacrol
6. Ketones. Carvone, menthone, pulegone. irone, fenchone, thujone, camphor, methyl
t
TI
ffi
Buds (cloves) Eugenol 85-95%
Clove Zanzibar, Steam nonyl ketone, metliyl heptenone lr
Madagascar, 7. Esters.
Cineole, internal ether (eucalyptole), anethole, safrole Sl
Indonesia 8. Lactones. Ooumarin
Steam Fruit Linalool, pinene h
,Coriander Central EurgPe, ilr
Russia
9, Terpenes. Camphene, pinene, limonene, phellandrene, "edten" {!,

Eucalyptus California, Steam Leaves Cineole 10, HEdrocarbons. Cymene, styrene (phenylethylene) tFl,

' (eucalyptole) lill

Australia
70-80% In living plants essential oils are probably connected with metabolism, fertilization, or pro-
Steam Leaves Ceraniol esters tection {rom enemies. Any or all parts of the plant may contain oil. Essential'oils are lound
Cetanium Mediterranean qr
30%, citronellol
countries in buds, flowers, leaves. bark, stems,'fruits, seeds, wood, roots, and rhizomes and ilr some trees
Cold poma,Je Flowers Benzyl acetate,
Jasmtne France, EgyPt, in oleoresinous exudates.
linalool, and
Italy
esters Volatile oils may be recovered from plants by a variety of methofls:a (1) expression, (2)
[,avender Mediterranean Distillation Flowers Linalool distillation, (3) extraction with volatile solvents, (4) enfleurage, and (5) maceration. The
area majority of oils are obtained by distillation, usually with steam, but certain oils are adversely
Peel d-Limonene
Lemon California, Sicily Expression
90%, citral affected by the temperature. Distilled citrus oils are of inferior quality; therefore they are
s.5-57 derived by expression. For certain flo*ers which yield no oil upon distillation or else deteri-
Florida, Expression, Peel d-Limonene orated oil, the last three methods are used. However, extraction with volatile solvents, a com-
Orange, sweet
California, distillation 90% paratively recent process, has superseded maceration (extraction with hot fat) for all practical
Mediterranean purposes und is replacing enfleurage. Solvent extraction is the most techhically advanced pro-
area cessand yields truly representative odors, but is more expensive than distillation,
.Stearn Leaves and tops Menthol 45-
Peppermint Michigan,
Indiana, etc.
90% and esters Disti,llation, usr.tally oith steam.. Flowers and grasses are normally charged into the still
Eteam, solvent, Flowers Geraniol and without preparation. Leaves and succulent roots and twigs are cut into small pieces. Dried
Rose Bulgaria, TurkeY
citronellol 75%
enfleurage materials are powdered. Woods and tough roots are sawed into small pieces or mechanidally
Steam Wood Santalol 90%,
Sandalwood India, East Indies chipped. Seeds and nuts are fed through crushing rolls spaced so as to crack them. Berries are
esters 3%
Steam Leaves Carvone 50* charged in the natural state, since the heat of distillation soon develops enough pressure to
Spearmint Michigan,
Indiana
6OVo burst their integument. The stills employed in factories are of copper, tin-lined copper, or
Enffeurage, Flowers Tuberose oil stainless steel and of about 2300 L capacity. They are provided with condensers of various
Tuberose France
solvent sorts, tubular ones being the more efficient, and with a separatoi for dividing the oily layer
extraction
Leaves Methyl from the aqueous cne. Although removable baskets for holding the material to be distilled
Wintergr"en Eastern United Steam
salicylate 99% are used, the better procedure seems to be to construct the still rvith a perforated false plate
(gaultheria) States
YIang-ylang Madagascar, Steam, solvent Flowers Esters, alcohols lying just above the bottom. Underneath this false bottom are steam coils, both closed and
Philippines extraction
aDorland and Rogers, The Fragrance and Flooor lndustrg" Dorland, Mendham, N.J'' 1977

488
490 Chap.27 Ftattancca,Flavotc,andFoodAddltlvu
perforated. In operating these stills, the charge is heated by steam in both the closed and the
open pipes, thus effecting economical steam distillation. The aqueous layer in the condensate
t."qru.rily in solution, valuable constituents, as in the cise of rose and orange flower
"^.ries,
oil, and is consequently pumped back into the still to supply some of the necessary water.
Steam distillation usually is carried out at atmospheric pressure. If the constituents of the oil
are subject to hydrolysis, the process is carried out in a vacuum. Much distillation for essential
oils is done-at the harvest site in extremely crude stills. These stills are converted oil drums
or copper pots equipped with pfpe condensers running through water tubs. The material and
water are charged into therstill, and a direct fire of dried material exhausted in previous
distillations i.s built r.nderneath. The efficiency is low, and the oil is contaminated with pyrol-
ysis products, such as acrolein, trimethylamine, and creosotelike substances.
'Ihe crude oils
obtained from the stills arb sornetimes further treated before use by vacuum-rectification, by
fractional freezing (e.g., menthol from Japanese'peppermint oil), by washing with potassium
hydroxide to remove free acids and.phenblic compounds, by removal of wanted or unwanted
,id"hyd.r and ketones through formation of the bisulffte addition,compounds, or by forma-
tion of specific insoluble products, as in the reaction of calciirm chloride with geraniol.
Expression by machine can yield an oil almost identical to the hand-pressed product, and
,is the method used eommercially. Of the hand-pressed processes, the sponge process is the
most important, since it produces the highesrquality oil. Here the fruit is halved, and the
peel trimmed and soaked in water for several hours. Each peel is pressed against a sponge,
anci the oil is ejected into the sponge, which is periodically squeezed dry. One person can
prepare only 680 g of lemon oil a day by this method, but it is still practiced, especially in
Sicily.
Enfleurage. The enfleurage process is a cold-fat extraction process used on a few types of
delicate flowers (jasmine, tuberose, violet, etc.) which yield no direct oil at all on distillation.
In the case of jasmine and tuberose, the picked flowers coritinue to produce perfume as long
as they are alive (about 24 h). The fat, or base, consists of a highly purified mixture of I part
tallow to 2 parts lard, with 0.6% benzoin added as a preservative. This method is no longer
used commercially.
Extraction with oolatile solDents. The most important factor in the success of this practice
is the selection of the,solveht. The solvent must (1) be selective, i.e., quickly and completely
dissolve the odopiferous components, bUt have only a miriimum of inert matter, (2) have a
low boiling point, (3) be chemically inert to the oil, (4) evaporate completely without leaving
any odorous residue, and (5) be low-priced and, if possible, nonflammable. Many solvents
have been used, but highly purified petroleum ether is the most successful, with benzene
ranking next. The former is specially prepared by repeated rectification and has a boiling
point no higher than 75oC. When benzene is employed, it is specially purified by repeated
crystallization . The ertraction equipinent is complicated and relatively expensive and consists
of stills for fractionating the solvent, batteries for extracting the flowers, and stills for concen-
trating the flower-oil solutions. The two types of extractors employed are the stationary and
rotary types.
In the rotary pro3"s the oil is extracted on the countercurtent principle. The 1325-L
steam-iacketed drums revolve around.a horizontal axis and are divided into compartments
by pe*o$ated plates.at right angles to the axis. About 135 kg of flowers is charged into the
first drum, along with 575 L of petroleum ether which hais already comq through the other
two drums. The drum and-its contents are rotated for an hour cold and for qn additional half
hour with steam in'the jacket. The saturated solvent is pumped to the recovery still, and the
flowers in the drum are heated twiie more, the second time with once-used solvent and the
last time with fresh solvent from the recovery still. The exhausted flowers are blown with
ThePerfumelndvdrY 497
steam to.recover the adhering solvent. About 90 percent of the solvbnt is boiled off at atmo-
spheriq pressure, and the rest is removed under vacuum. After the solvent i$ removed in either
p.o""rr, th" semisolid residue contains the essential oil, along r,r'ith a quantity of waxes, resins,
and colbring material from the blossoms. This pasty mass is known as conclete. In turn it is
treated with cold alcohol in which most of the wax and resin are insoluble. The small aiaount
of unwanted material that dissolves is removed by cooling the solutiou to -20"C and filtering
it. The resulting liquid contains the essential oil and Some of the ether-soluble color of the
flower and is known as an ertract. When the alcohol has been removed, an obsolute remains
In some oils there is a large quantity of terpenes. This is especially true in the case of lemon
and orange oils, which have as much as 9O% d-limonene in their normal composition. Not
only are terpenes and sesquiterpenes of exceedingly little value to the strength and character
of the oils, but they also oxidize and polymerize rapidly on standing to form compounds of a
strong turpentine-like flavor. Furthermore, terpenes are insoluble in the lower strengths of
alcohol used as a.solvent and make cloudy solutions which are cleared up only with difficulty'
Hence it is desirable to remove terpenes and sesquiterpenes from many oils. Such an oil, ,!l
orange, for example, is 40 times as strong as\he original and makes a clear solution in dilutb
alcohol. The oil has now very little tendency to rancidify, although it has not quite the fresh- ti
ness of the original. These treated oils are labeled "tsf" (terpene- and sesquiterpene-free).
lr
{l
Because each oil has a different composition, dete.rpenation requires a special process. Two h
methods are involved, either the removal of the terpenes, sesquiterpenes, and paraffins by
{t
fractional distillation under vacuum, or extraction of the more soluble oxygenated compounds *t
(principal
^ odor carriers) vrith dilute alcohol or other solvents.
Because 6f the complex nature and the high price commanded by so many essential oils, a fi
great deal of adulteration, or sophistication, is practiced. These additions were formerly
extremely hard to detect in most cases since, whenever possible, a nrixture of adulterants is
used thai does not change the physical constants of the oil. Common agents used are alcohol,
cedar oil, turpentine, terpenes, sesquiterpenes, and low specific gravity liquid petrohums.
The advent of so many esters of glycol and glycerol on the market increased the difficulty of
detectiorl, since these compounds are colorless and practically odorless and in the right com-
bination can be made to simulate almost any specific gravity and refractive index specifica-
tions set up {or the oil they are intended to adulterate. The modern use of gas chromatogra-
phy (GC) has made it possible to deiect easily even small amounts of adulterants. Rose oil
may be sophisticated with geraniol br a mixture of geraniol and citronellol; wintergreen and
sweet birch oil are mixed with large amounts of synthetic methyl salicylate; and lemon oil is
often "stretched" considerably with citral from lemon grass oil.
lsolotes. Isolates are pure chemical compounds whose source is an essential oil or other
natural perfume rnaterial. Notable examples are eugenol from clove oil, pinene from turpen-
tine, anethole from anise oil, and linalool from linaloa oil (bois de rose).
SyN?IIErTCS AND SEMISrNTIIETICS USED IN PE&FAMES AND FLAVO&S.S N4ore and more
important constituents of perfumes and flavors are being made by the usual chemical syn-
thetic procedures. Compositions containing predominantly inexpensive synthetics now
account for more than 50 percent of the fragrances used in perfumes. Some constituents are
chemically synthesized from an isolate or other r.atural starting materials and are classed as
sPoucher, Perfumes, Cosmetics and Soaps, vol. II, Wiley, New York, 1974; Clark and
Grande, Study of Odor Variation with Structural Change, Cosrnet. Pertum.90 (6) 58 (19?5);
Chemicals from Trees, CHEMTECH, 5 236 (1975).
 492 Chap. 27 Fragrancea, Flavorc, and Fcioi! Addlttvcs
The Perfume Industry 453
semisynthetics. Examples ar.e vanillin, prepared from eugenol from clove oil; ionone, from
citral from Iemon grass oil; and terpineols, from turpentine and pine oil. Some of the signif- material, or the Hassmann-Reirner synthesis, where coumarin-3-carboxylic acid is produced
icant synthetics are discussed below. The examples presented are grouped under the'most as an intermediate. Over 450,000 'kg is produced per year.
important chemical conversion. Diphen,Jl oxide, or ether, is largely used in the soap and perfume industries because of its
great stability and strong geranium odor. Diphenyl oxide is obtained as a by-product in the
Condencation procesieoa (Fig. 2Z.l), Coumarin occurg in tonka beans and 65 other manufacture o{ phenol from chlorobenzene and caustic soda.
plants, but.the economical source is the synthetic. It is employed as a fixative and enhancing
agent for essential oils and tobacco products, and as a masking agent for disagreeable odors 2C6H5OH: CoHsOCoHs * H2O
in industrial products. The synthetic product may be preparedT in a number of different
ways. One method utilizes the Perkin reaction: Ionone and its homologs possess the so-called violet type of odor, thus constituting the base
of violet perfumes. These compounds, however, are indispensable to fine perfumes, and there
are but few which do not contain at least a small perbentage of ionones. Annually, about
225,000 kg of ionones is produced. Because of the high price of the natural oil of violet, this
O::'#ffiF @:x:'HCooNa - @;-:," was'one of the fiist essential oils synthesized, although it has since been found in certain
obscure plants. The olfactory properties of ionone are due-to the presence of dl-a;ionone and
Salicy-laldehyde, acetic anhydride, and sodium acetate are refluxed at 135 to l55oC. The B-ionone. Their manufacture involves two steps: First, the pseudo-ionone is prepared by the
reat'tion mixture is cooled and washed. The coumarin is recovered by solvent extraction or condensation of citral obtained from lemon grass oil. This is followed by an acid ring closure,
distillation. Other important methods of coumarin preparation utilize o-cresol as the starting and the commercial ionone is purified by distillation. Commercial ionones are $enerally mix-
tures with one form predominating, although separations are sometimes made through bisul-
6Process-studded
Plant: Key to Fragrance, Chem. Eng. 6i (4) I12 (195g) [ite compounds.
7ECT,3d ed., vol. 7, 1979, p.
196.
,r4., ,r",, Hrc,..,,,uH,,

--c CH cH, --c

HC" -CHo I HC" CHCH: rtH(lo(tH-J
I tt + C:o 'i.11-.?]-,
\aoH I ll H2so{,

Hrc-'cH,
-l- cH. cH,i Hri_-CH,-c- cHr
roao

r Cirral P*udo.ionone

H.C
'\,/ CH" H"C CH,,

"'|/.c
C
PRETREATMENT
PLANT H"C
f H,C
-l eCH:
_ l aTEntaLS.-Crushing, grinding, CHCH:CHCOCH CHCOCH;,
chopping, eic i"*^ ll
H,C.
' -cri-_\'.- CH" H,C.
'-c, -C CH,,
-
SOLVE NT
I a.lonone p.k,ione
EXTRACTION

Cinnamic aldeh1de has a cinnamon odor. As it oxidizes in air to cinnamic acid, it should
SYNTHES IS

r ru
CHEM ICA L
r"r n],,r'i 5 iai e S
._-.-+ Or i n, h y d ro I e no ri o n,
d,o I io
be protected from oxidation. Although this aldehyde is obtained frorn Chinese cassia oils, it
condensolion, ocelylolion, is Synthesized by action of alkali upon a mixture of benzaldehyde and acetaldehyde (Fig.
polymerizolion, etc.
27.2). The production is about 365,000 kg per year.
-
ANIMAL
PRODUCTS
C6HsCHO + CHsCHO.*C6HsCH:CHCHO * H,O
PURCHASED I,IATERIALS
-roR hESALE This and most other products for fragrances must be purified, for example, by vacuum frac-
Essentiol oils tionation (Fig. 27.3).
Chem icols
Florol obsolutes I

Florol concrels
I
I Esterification Processes. Benzgl berizoalr has a faint aromatic odor, boils at 323 to
324oC, and is a fixative and a flavor:ng material. It occurs naturally in balsams (Peru, To16)
}S,-27t!tOu1!i1e flowchart for the manufacture of perfume 3nd flavoring materials. [Ind. Eng. Chem.
53 (6) 422 (7961); courtesg oJ Filtzsche Bros.l t
but is,'prepared commercially by the esteriffcation of benzoic acid with benzyl alcohol or by
the Cannizzaro reaction with benzaldehyde.
 !:
!
i.r
The Perfumc Indurtty 495 '],ii$

494 Chap..z7 Fragrnncee, Flavore, and Food Addlllvu :&

,'$

il

Two esters ol salicElic actd \o-hydroxy benzoic acid) are very important commercially in
benzoldehyde,
'the perfume and flavoring industries. About 160,000 kg of am,ll salicAlate is used annually
colol ysl
in a variety of perfumes, because of its lasting quality and low price. About 1.8 X 106 kg of
t"rrethAl salicrJlate (synthetic wint'ergreen oil) is consumed annually as a flavoring ingredient.
'IheSe esters are prepared as follows: Carbon dioxide and sodium phenate are reacted under
pressure to obtain the salt of phenylcarbonic acid. This salt is isomerized to sodium salicylate
by heating to 120 to 140oC, The esters are made from-the acid and the proper alcohol.
BenzEl acetate (C6H'CH2OCOCHs) is anothet widely used ester because of its low cost
and floral odor. About 450,000 kg is sold annually for soap and industrial perfumes. It is
prepared by esterification of benzyl alcohol, by heating with either an excess of acetic anhy-
Wosle lh gher polymers) dride or acetic acid with mineral acids. The prod.uct is purified by treatment with boric acid
REACTOR NEUTRAL SEPA. WASHING FRACTIONAL and distilled, giving a purity of over 98%. Large amount s of benzgl alcohol are employed in
]ZATION RATION I DISTILLATION pharmaceuticals, iacquers, etc. (about 1.8 X 106 kg per year). This alcohol has a much weaker
Fig..27.2. Flowchart for cinnamic aldehyde'production by aldol condensation. (Fritzsche Bros Inc.) odor than its esters. It is made by hydrolyzing benzyl chloride'
{1

I 'li,
{ Grignord Processes. Phenglethyl alcohol has a roselike odor and oocurs in the volatile {.
oils of rose, orange flowers, and others. It is an oily liquid and is much used in perfume i
I
formulation, more than 450,000 kg being sold annually. Phenylethyl alcohol can be made by
i
a number of procedures; the Grignard reaction is used generally:
T

i;
c6HrBr -]"],EI! c.H rMgBrtU'aur, ar rarroMgBr -9f c6Hs . cH2cH2oH ri
,i
However, the Friedel-Crafts reaction is outlinqd in the flowchart in Fig. 27.4 andfollows the
leaction

jEgc6Hs.
CoHo + (cHz)2o cH2cH2oH
BnEne Ethylene
oxide

Hgdrogenation. See Fig. 27 .5 f or citroiiellal from citronellol by Raney nickel hydrogen-

ation at 1375 kPa.

CH2-C(CH2 )3-CH-CHr-611, gg --;;i CH2-C-(CH2)3-qH-CH2-CHO

CH: CH: CH: CH:

Citroneliol Citronellal

Nitration Processes. Artificial musfts comprise a number of products not identical lvith
the natural musk, which derives its odor from macrocyclic compounds. Nitro musks are prac-
tical and economical substitutes for this expensive natural fixative, and more than 90,000 kg
o[ musk xylene alone is manufactured annually. The reactions for the three important com-
mercial artiffcial musks are

MUSX AMBNETTE
oH ocH3 ,
rAl KoH aAt"
rlrtr% (ctt.).co, (cHa)3c HNor
.r, ffi
-.QCH,
(cH3)3cal-\NO,

Fig. 27,3. High-temperature vaicuum fractionating equipment. (Frltzsche Bros.,

\2.n. V.r, Atct3
v.r.NO,
Inc.)
 Thc Pcrfitme Induby 457
N6 Chap.27 Fts,t,|ance., Flavoeol hnd trood Addltlvat
Hydrogen
Elhylene
oxidb

PRESSURE
VESSEL

BATCH
OISTIL LATION
COLUMN

Fig.27.5. Hydrogenation under pressure of lB80 kPa to

convert citronellal to citronellol. {Chem. Eng. 65 (4)
(1958); courtesA ol Van Ameigen Haebler.l
Fig. 27,4. Phenylethyl alcohol formed by the Friedel-
Crafts reaction. lChem. Eng.85 (4) 113 (1958): courtesg
ol Van Amertgen Haebler.l OH OH OH

MT]$(, XYLENE AND MASK I(,,TONE

o*"
\7,
CHrCH:OH,
1fiot'"
V
uou (:.Hsto2,
[6)"t''
\.,-
CH:CHCHT CHO
CH, , tiugenol l*ugenot Vanilin.

?0% Hzso., o-uANo. 2. From.lignin8 through an alkaline pressure cook at g00 to 1400 kPa for }6 to I h. The
C6H/CH3)' -l!ffig- c6H3(cH3)2. c(Crr.l.
ffi [9 ar,
vanillin is puriffed through the sodium bisulfite compound and extraciion with benzene or
n.X;rlenc ,.rrn isopropanol (Fig. 27.6). Most of the vanillin on the market is made this way.
NO, 3. From phenole or o-chloronitrobenzene through guaiacol, following the usual synthetic
lusk xvr'ne procedure.
I cH.
Heliotropin, or piperonal, has a pleasant aromatic odor resembling heliotrope. It is pro-
qP, . c6H2(cH3)2.c(cH3)3.cocH3
_r___r,r _,___r
**',,,..o'*fAtotn' duced from safrole by the following reactions:
,ltct. "0,.2r",13/2 (CH.)3C\2CH,
Ne',cr'o7 o-Y,A\
NO,
..;"YA /.?YAr tq']g].r"
: ".,Tj:,1:,,,.

*n:'' tr:'S{).,
[:--r!2cu,cH :.HCH3 *#
CH,
Orkl,irion Procecses. Vanillin is one of the most widely used flavors, more than ti80'000
k-g/ye* being man$factured. It is used as a flavor in perfumery and for deodorizing manu-
ii-#; jffi,;!, i*,.#;
f.-cturud goods. Many processes have been employed in its manufacture. srch as the -sCIil
following:
I
,r" US. Patent 3,054,659 (1962); ECT, Sd ed., vol. 14, 1981, p.
esch*yzer, Die Fabrikation pharmazeutischer
i 806.
I
und chemischtechnischer Produkte, Sprin-
l.From eugenol from oil of cloves, through isoeugenol, followed by oxidation to vanillin, ger, Berlin, 1931, pp. 205-2@.,279-288.
using nitrobenzene as the oxidizing agent:'

t
496 Ch.p. 27 Fllag"anccq Flavota, and lod Addlttvct The Perfumc Ind.uatry 499

rernoved saccharin from the Generally Recognized as Safe (GRAS)ro list and required that all
food and beverages containing saccharin have a warning label. A study was undertaken by
the National Academy of Sciences to determine.its safety for human corisurirption, but it did
not provide definite conclusions.ll In Ig77 the FDA restricted the use of saccharin, a decision
based on limited test data on laboratory animals. Saccharin is manufactured, employing the
itollowing reactions, with a 90 percent yield on the last step.

.."t)'.:rll' .' .fill:i;,:lt* Fractionariv precipitated

"Tik:'
o
il
:ooN3
^t'
Fig. 27.0. Vanillin from lignin. lChem. Week 89 (37.) 103 (1961)'l ,,.(iri.iL6H4sozcr 5 i*Ii' '' (Y( a,idili.d ,/--Y"-N,
o.crtr.,r.^p rso2NH2
\---\so?NHz
h.at.,l llll
\;-srt,
which
tntsaldehgde is a colorless oily liquid with an agreeable odor resembling coumarin' o-Toluene sulfochloride,60 % o,Sulfamvlbenzoir arid

in mixtures. It is made by the oxidation of anethole (the

i, i"r"fop.a anly after dilution and
of anise, star anise, and fennel oils). Anethole has been obtained recently in An alternaie synthesis from an.thranilic acid is clajmed to yield a prodrrct with less bitter
chief constitueni
this country at very low cost from higher-boiling fractions of pine oil' .r Itertaste

-Su
7--i r",c,,o,
-Fn'V
-ry'
[7-\l
\/itt: cttctt. cHo
o.),rH,CuH,CooH

'Anthranilic
*ffi oto*"
-- -sorcr
fi
oi
acid Saccharin
and as an
Benzaldehyda is used as a flavoring agent, as an ingredient inpharmaceutieals, f
it is produced by several methods and in Miscellaneous Processes, Aspartame,t2 l-aspartyl-l-phenylalanine, is 200 tim6s
intermediatein chemical syntheses. Commercially, I

grade is largely used as an intermediate in sweeter than sugar. It has recently won limited approval from the FDA for use in some foods,
i;;;r"d"r, technical and ieffned. The te6hnical
and for use in soft drinks. It now is able to compete in the nonnutritive sweetener market
aldehyde, and dyes. Most
the slynthesis of other chemicals, such as benzyl benzoate, cinnamic
T

with saccharil, which has been on the market fqr many years.tB The regulation that requires
oiltl tu"t"i"al grade is made by direct vapor-plra_s1 oxidation-of toluene,.although someForis
by alkaline oracid hydrolysis' a warning label on saccharin-containing foods will expire in 1g83, and, uniess it is'extended,
-"a" Uy chloriniting toluene to Lenzal chloride, followed aspartame will be the only accepted'nonnutritive sv/eetener on the market. Saccharin con-
perfume and flavoring use, the reffned, chlorine-free grade is required, which is economically
of toluene. 'ihis oxidation is sometimes carried sumption is about 7 g per capita per year, and 3 to 4 x I03 tfyear is produced, so the market
iroduced by the direit vapor-phase oxidation
is large.lst A combination of saccharin and aspartame is sweeter than either compound alone
out in the liquid Phase.
and aspartame has no objectionable aftertaste as saccharin does. Aspartame, however, is not
VAPON PIIASD very stable to heat and liquids, but it will retain its sweet taste in soft drinks for about 6
rnontl-,s.
coHscHsff"rrr"ro + Hro AH = -382kJ Terpineols are among the cheapest synthetics and are widely used in soap because of their
*'oodsv and floral odors. Formerly, all terpineols were made from turpentine oil, which con-
srsts largely of a-pinene, but recently pine oil has become an important source. Terpinecils
Itis claimed that a catalyst mixture of 93% uranium oxide andTVo molybdenum
oxide gives
relatively high yields. - tHrll,
CR^--toncept and Appiication, Food TechnoL 29 (t)48 (i975)
rrNational Academy o[
LICIUII' P'IAIJE Science Report No. PB-2381'37/AS. Ig75 lavailable from National
Technical Information Service, Springfield, Va.),
C6HsCHs + HrO i2For saccharin and aspartame,
Food Eng.54 (7) 77 (1982).
-;*C6H5CHO
'*Sugar Substitutes Seek Sweet Smell of Success, Chem. Eng. News 52 (44) g7 (lSi4), Food
Sacclnrln l)SP (o-benzosulfimide) is approximately 500 times sweeter than sugar' It has Ens.4S (8) 27 (1974).
r8"t : looo kg.
been widely used by diabetics and in diet drinks and foods. However; in 1972 the FEA
 TheFlavorlng,Indurt"y 501
500 Chap.27 trl.tr:arncar,'FlavorqtndFoodAddltlvea

may be manufactured direetly in a one-step process from

pinene by reaction with sulfuric Table 27.3 Types of Perfumes
acetone for 6 hat 35io 40"G. The product is purified by fractional distillation' The
Classification Manufacturer Trade Name
""ii ""a
tru*rt"p -utt od has en advantage in that the purification of the intermediate, terpin hydrate'
is easiei than that of terpineol. ierpin hydrate is formed
by reacting pinene with dilute sul- Straight floral Coty Muguet des Bois
The purified hydrate is dehydrated to terpineol bv oxv- Floral bouquet Revlon Charlie
furic acid #5
"nd "n "*,rkil;i;;"g""i.
acids. Tefpiieols are separated from pine oil by fractionai distillation' Aldehydic floral Chanel Chanel
;;;;;J;"ilxylic
' Mentholhds long been exiracted as the levo from from oil.of Japanese peppermint and Oriental Coty L'origon
Chypre Factor Acqu4marine
pure optically
,J i; cigiarettes "id rrr"rry other products as an antiseptic cooling flavor The Woody Jovan Sport Scent
active for-m is made by Ciidden io. fro- B-pinene (from turpentine)'t4 This compound is Green Shulton Old Spice Herbal
to make B-citronellal' catalytical conversion Citrus' Jovan Eau Fresh
hydrogenated, isomerized, and dehydrogenated
Cougere Dana 20 Carats
yields l-menthol, after fractional distillation and
;;;r;", isopulegol,
"rd'hyarog"r,atioi Canoe Faberge Brut
Musk Musk Oil
-''ih,
crystallization
only slightly modified from that of aldehydes but
Jovan
Shulton Old Spice
o"rtol" of aldeh,ldes have an o-dor Spice
soaps, which are very difffcult to
hare great alkali re,istance. Flence these acetali are used in
perfume.
aromatic firms. As the perfumer's skill and resources increase with experience and research,
new equipment is developed for identifying fragrance components, even in trace quantities,
Perfrpfre Formulation such as infrared and ultraviolet spectrographs and chromatographs. Eventually, such instru-
mentation'will be perfected to expedite production, but currently the perfumer's nose is
acrual example of a compound perfume sin rilar to
a widely sold product (Table 27'2)
t1'ki
regarded as the.more discriminatory in arriving at a creative blend of exotic ingredients. Even
4it""i"r ii";r;i;;r ";ponents that haue been discussed and shows- their use in a blended he or she does.not know precisely what will make one formulation successful where several
oio* methyl ionone, and bergamot oil. Although hundred others may fail. Furthermore, after months of trial to attain certain objectives, a
prJ"". TheToundatio., are from eugenols,
may contain 50
fragrance
ihe formulation given in the table sho*s a 1o*er number, a single consumer panel may be unenthusiastic about the product. High quality from batch to batch
subcompounds; in fact, as many as 300 ingrediertts may be is routinely ensured by standard tests, such as speciffc gravity, optical rotation, refractive
to l0O different compounds and
appr.gimately 500 natural and 30oO synthetic oils are available for perfume '
index, acid number, and ester number. Provided success is met thus far, "the name, the pack-
"r.J
production.l5 age, the advertising must all be perfectly orchestrated" with the product.
The psychological effect of odor is successfully used primarily to increase customer appeal.
do- not manufacture their
F}Ail,rANCE IUALITL. The majority of domestic perfume houses Perfumed merchandise outsells its odorless counterpart by a large margin. An insurance com-
their synthetics custom-made by
o*n ,""rtr, they usually import natural floral oils and have pany increased its sales of fire insurance overnight by sending out advertising blotters treated
to simulate the acrid odor of a fire-gutted building. All kinds of paper are now perfumed to
f'"* 'frees, CHEMTECH 5 (4) 235 (1975)'
"CI[Itlt increase sales appeal. Table 27.3 lists the main types of perfumes.
Fragrance-Front-Runners, Chem'Week 86 (I) 24
(1960)'
'sAerosols;

Table 27.2 Cornposition of a Perfume THE FLAVONING INDUSTRY

Component Grams Component Grams
There are oniy four basic flavors which the nerve endings in the taste buds on the tongue can
Synthetics detect: slfeet, saur, salt1, and bitter.to The popular conception of flavor, however, involves
Essential gils 27.5
Sandalwood oil l0 Coumarin
the combination of these four basic stimuli with concurrent odor sensations. Apple,' for
Vanillin 20
'Bergamot oil u7.5
., 40 Benzyl acetate 30" instance, tastes merely sour, with a trace of bitterness from the tannins present. The main
YlanS-Yl&ng ou 2.5
Petigrain oil l0 Oleoresin, oPoPanax concept received of an dpple is due to the odor of acetaldehyde, amyl formate, amyl acetate,
l0 Balsalns (resinoids) and other esters present in the volatile portion. The principles of perfume blending also hold
Orange flower oil 5
otto l5 Tolir
Rose : good for flavor manufacturing. The best flavoring essences are natural products altered and
20 Peru
Jasmine absolute 70 reinforced where necessary by synthetics. In addition to alcohol as a vehicle, glycerin and
lsolates '
Benzoin
90 Animal ftxative, castor tincture l: l0 12.5 isopropyl alcohol are used for liquid preparations, dnd emulsions of bland gums, such as
Eueenol (from clove oil)
San-talol (irom sandalwood ) I5 Synthetic fix.tives tragacanth and acacia (gum arabic), for pastes. The same fixatives are employed, especially
Musk ketone 32.5
Semisvnthetics 12.5 vanillin and coumarin; animal types are r1sed sparingly. Many esential oils ffnd application
-Isoeusenol
(from eugenol) llb Musk ambrette
450 kg
15 Vehicle, ethyl alcohol
ilelioirbpin (f rom saf role)
Methyl ionone (from citral) ?,37.5 r6Hornstein and Teranishi, The Chemistry of Flavor, Chem. Eng. News 45 (32) 9S (1967)
 Thefllavoilnglnduslry 503
502, Chap.27 Fratrances, Flavors, and Food Addillvea
Preparation o! oanill.a ei,xtract. One hundred pounds of a blend of Mexican and Bourbon
in the flavor industry, the more common being spice oils, citrus oils, peppermint, and spear- beans is finely cut up and macerated cold, with three'successive portions of 35% ethyl alcohol
mint, Alpost all peqiume synthetics find acceptance, plus a number made especially for fla- of 4E kg each. These extracts are combined to make a fine vanilla extract. Other solvents may
propionic,
vors. The esters;f ethyl, methyl, arnyl, propyl, and benzyl alcohols with acetic, f. ,sed and the extraction carried further, but the product is coarsei and less desirable as a
butyric, salipylic, caproic, for*i", valeric, and anthranilic acids are widely used to character-
fine flavor (cf. Fig. 27.6).
ir" irr.ii flavors. As *ith flo*"t perfumes, many chemical specialties keynote individual fr.it
aromas. The 7-lactorre of undecylenic acid is a true representation of the
fresh odor of a cut
CfiOCOL/ITEANDCOCOA. The cacao bean, the seed of Theobrorno cacaoL, grows in equa-
peach. A strawberry base is the ethyl ester of methylphenylglycidic acid, although it is
not a
Anethole has the taste of'anise and torial areas on the tree in podq with from 30 to 60 beans. The pods are spiit open, and the
true effect and pariakes of a sornewhat unnatural tone, watery pulp containing the seeds is allowed to ferment in boxes from 2 to 7 days, which, in
pineapple
licorice, benzyl acetate tastes like raspberry or cherry, and allyl caproate is used for additio; to liquefying the pulp, kills the embryo (46oC), reduces the toughness of the bean,
compounds used for flavorings are cinnamaldehyde (cinnamon),
flavors. Other common
frees theobromine from the glucoside, and reduces the astringent tannin content. This fer-
diacetyl (butter), menthol (mint)' and isoamyl acetate (banana)' mentation is necessary for flavor in the final product. The fermented beans are dried and
shipped to manufacturing centers. The beans are then heated in rotary loasters between 105
120oC, which develops the true chocolate flavor and aroma, relnoves unpleasant tannins
,Vafural Fruit Concemtrates "nJ
and volatile matter (butyric and acetic acid, organic bases, and amines), dextrinizes the starch,
as those used for
and embrittles the husk. The roasted beans are quickly cooled to prevent overroasting,
Although the essential oils used in flavoring are the same grade and sor'rrce cracked in a conical mill, dehusked by a winnowing air stream, and degerminated. This prod-
Because of the large
f.rfr*""r, fruit flavors are handled in a somewhat
(from
different rnanner.
in the t"run, to 90% in the straw- uct is knoq.n as cacao nibs. To work up the cacao product into chocolate, the "modern method
percentage of water in most common fruits 75%
is to grind sugar in a closed-circuit disintegratcr and the nibs in a separate water-cooled two-
of considerable amounts of sugar and other easily fermented mate-
berry) and the presence
stage disk miil with closed-circuit removal of the fines. The two are then mixed. This method
rials, special processes must frequently be employed, such as the
following:
p.odu"", a fine, uniform product. The paste is run through a'concher, which is a granite bed
Distillation and. ertraction of the fruit, The tipe fruit is stoned and comminuted lt is with reciprocally acting granite rollers. It reduces the particle size to an average of less than
then subjected to steam distillation and rectification rintil all the aroma is concentrated
in a I pm. It is steam-heatedlo run at 57oC or can be allowed to heat itself by friction (50"C).
small portion of the aqueous distillate. This portion is then extracted with low-boiling petro- Milk chocolates are prepared by adding condensed fresh milk or milk powder to the mill
product has a cocoa-butter content of 30 to 35% and, not less than
le,r* eth.r, and the eiher re*oued under vacuum to leave an es$ence, or quintessence' of (melangeur). The finished
tie fruitused. Cherry, apple, strawberry, and raspberry are.treated by this
method. lyVo milk solids. For cocoa, the roasted and ground beans ate subjected to pressure in
In the and filtered juice is extracted hydraulic presses to remove some of the fat content. Whereas originally roasted be4ns contain
Ertraction of the iuile. this system expressed
directly without previous distillation. Occasionally, the juice is allowed to ferment
shghtly SS% fat, the product remaining after this treatment has the fat reduced to20Vo, and is known
before extraction. This is supposed to result in a fuller flavor' as cocoa. The removal of fat makes a beverage that is not too rich and one in which the fat
Concenbation of the iitie, The expressed and filtered juice is concentrated in vacuum does not separate on top.
evaporators with a llow i"g."" o[ heat until the water is largely driven off
and the sugar
concentration is high enough to inhibit bacterial grorrth (60%). This type
of concentrate often MONOSuDTUM GLU'.1AMATEIMSL, COOH\CHTtTCHQ|H)COONaL This compound is an impor.-
h"r, "1^,,," o.'"oo.-k"d flaror, especially in the case of the strawberries An alternative method tant flavoring agent, yet has no flavor of its own. It accentuates the hidden flavors of food in
of concentration is freezing. Afier reducing the temperature sufficiently, the mush of prac- which it is used, Reports that the use of MSG in foods is harmful were denied by a National
ir.rlly pur" water ice is filtered off, antl the partly concentrated juic"e is refrozen and refiltered Academy of Science-National Research Council report in 1971.17 In 1974 the Food and
until the requisite strength is obtained. This is the optimum mcthod of producing concen- Agricultural Organization of the World Health Organization approved the use of MSG as
trates, sinceihere is littie injury from heat, and the slight off-flavors from oxidatiort can be safe. Glutamic acid exists in three forms, but only the monosodiunt salt of L-glutamic acid
avoided by running the process in an atmosphere of carbon dioxide has a- flavor-accentuating capacity. Although glutamic acid is a constitpent of all cornmon
proteins, the economical sources have been wheat gluten, corn gluten, and Steffens filtrate.
,ANTLLA. .The vanilla bean is grown principally in Madagascar, Tahiti, and Mexico' It is the When Steffens beet-sugar wastes are used, the principal steps involved are (I) concentration
immature fruit of the orchid Vanltli planit'olla and is cultivated as a vine on trees
which and collection of the Steffens filtrate, (2) its hydrolysis, usually with caustic soda, (3) neutral-
support it. The pods are picked when they are just starting to turn frorn a uniform green to ization and acidification of the hydrolysate, (4) partial removal of the inorganic salts, and (5)
yeilo* at the tip and have a rather disagreeable odqr. The green pods undergo a curing crystallization, separation, and purification of'the glutamic acid. MSG is made from the acid
irEatment of from 3 to 5 months'duration. The cured bean is pliant, shiny, and
dark-colored. as described above. The pr"r".,t production of MSG is largely from fermentation,r8 and a
The odor has become full and rich, and the treatment may have left white aromatic crvstals
What happened is that the glucoside glucovanillin, present in t'Chem. Eng. Neus 49 (28) 17 (197I).
on the outside of the bean. has
the bean, has been acted upon by a ferment and split into glucose, vanillin, and other
aro' rENew process es, Chem. Eng. 69.(16) 17 (1962); Ind. Eng. Chem. Annual Unit Processes
matics. Substances identifiei in the vanilla bean are anisic acid, alcohol, and aldehydel 'an- Reviews: Fermentation, from 196I on; Hoelscher, Feimentation, chem. Eng. 7l (8) 9r
illic acid and alcohol; cinnamic acid and its esters; vanillin' eth;'l vanillin' and possibly other (t964); ECT,3d ed., vol. 2, 1978, p. 410.
homologs of vanillin.
504 Chtp. 2E Frryrtncoa, Nlloer., r,ed Food Addltlvcc Fmd Addltlves 505

flowchart is presented inEig.2i.7, Several U.S. companies have developed their own micro- Table 27.4 Typical Flavors
biological process or obtained it frorn the ]apanese. The raw material is frequently dextrose
Artiffcial Fruit Flavor for Chewing Gum
oo rulnr. Ho*"r"r, the jlpanese are using a synthetic process based on acrylonitrile.

Fl av o r- E ssenc e F or mulati onte Heliotropin 0.05 Oil of lemon 5.00

Ethyl vanillin 1.00 Oil of tangerine 5.00
Vanillih 2.00 Elhyl acetate I6.40
Formulas are given in Table 27.4for a fruit,flavor used in gum manufacture and a natural Aldehyde C16 0.55 Ethyl butyrate r5.00
apricot flavor. These show how a well-balanced flavor may be made up of na,tural products Oil of cloves 1.00 Isoamyl acetate 10.00
Isoamyl butyrate
reinforcbd with suitalle synthetics as well as a wholly natural formulation. Many formulas Oil of peppermint 2.00 5.00
C)il of orarrge 37.00
are to be found in print which consist mainly of esters of synthetic origih. These are harsh
and unnatural, and, in.many cases, the only resemblance'to the original is in the designation Naiural Apricot Flavor
of the flavor.

Apricot juice conc 99.6 Oil of orange 0.1

Absolute carob 0.1 Oil < f petitgrain 0.05
FOOD ADDITIVES Vanilla extr act 0.1 Oil bitter almond 0.05

"The food revolution in progress since the turn of the century almost deffes description. The
and loaded refrigerator trucks and railroad cars, in magnificent food stores and, finally, in
evidence is all aroundus-on fertile farm lands, and in lush orchards, among grazing herds kitchens and on dining tables at horne or in restaurants."20 The food industry; estimated at
reMussinan, Analytical Chemistry and Flavor Creation, CHEMTECH i0 (I0) 618 (1980)
over $2(D X IOe yearly, is the country's largest business. The average family spends approx-
imately l8 percent of its income on food. (See chap, 25, Food and Food By-Product Pro-
cessing Indr:stries, for details on the size of this industry.) Food additives are those chemicals
Sugor
amfronio combined with foods by the manufacturer to effect certain modiffcations involving preser-
Olher rolids
lnoculohl vation, color, Ilavor enhancement, and stabilization, which have helped 1o make an astound-
ing improvement in our food supply, as well as alleviating v.rork in the kitchen. Additives are
as old as history itself, spices, for example. Intentional odd.itioes are substances added in
caiefully controlled amounts to preserve the quality of food, improve its nutritive value, or
add flavor, for example, MSG (Fig. 27.7). Common kitchen staples such as vinegar, starch,
and salt are in this category. Incidental addltiDes are those that, although havipg no function
in finished food, become part of it through some phase of production, processing, storage, or
packaging.
By-Ptoduct The food additives have been separated into 52 categories.2r This list ranges from acidu-
moiher liquor
lants, anticaking (drying) agents, baking aids (yeast foods) through flavors, flavor enhancers,
starch modifiers, nonnutritive sweeteners to preservatives, sequestrants (chelating agents), sta-
oeeoiorizrr
biiizers, r,itamins, and wetting agents. The main classifications22 are colors, 3 percent; flavors,
l6 percent; enzymes, 8 percent; acidulants, 8 percent; nonnutritive sweeteners, 2 percent;
surfactants, l0 percent; antioxidants, 3 percent; preservatives, 4 perceflt; flavor enhancers, 7
percent; vitamin supplements, 3 percent; and nonspecialty additives su'ch as soy concentrates,
carrageenin, algrnates, and le.avening agents, 36 percent.
Commonly used additives include chemical preservatives like propionic acid and benzoic
acid; Lnffers and neutrohzing agents, such as acetic acid and sodium citrate; emuls$ging

Tolproduce I tj of MSG' HrO, the following materials and utilities are required:
wFood Addltloe$ Coder, 1972, Manufacturing Chemists Association; Furia, Handbok of
Sugar. 1.5-2.5 t Fuel 46.4 MI Food Addtttoes, Chemical Rubber, Boca Raton, Fla., 1968; Fernandez, Mixing Technology
Electricity 79,200 MI Direct labor 17.6 wort-h
and Food, Nea Eng.3 (11) 52 (197a); ECT,3d ed., vol. rI, 1980, p. 146.
monocodium glutarnate ptoduction by fer,mentation. (Intenwttor,,,,l Mlnerals
ItFood Ingr,edients Dl,recton4, Intechmark Corp., Palo Alto, Calif.
Sig i?.7. Flowchert of I

ad Clpm. Corp.) DAnother Checkup for Additives, Chem.Weekl2T (17) 29 (1980).

,,
 I

Foorl Addlrlves 5O7

506 Ch.P.27 F"agi.nccc,flavorc,andFoodAddltlvet

nonnutfitioe iu)eeteflers , such as saceha rin; nutfient , among which Fleath, H. B,: Source Book of Flaoors' Avi, Westport, Conn , I98I'
egents likepolysorbates;
.$

Heath, H, B.: Flarsor Technology, Prod.ucts and. Applications, Avi, Westport, Conn , 1978
other vitamins; a\d thickdners like agar'agar and acacia' Here should j"lll*k, J. S.: The LIse of Fragrance in Const mer Products, Wiley-Interscience, New York, 1976.
"i" "r""rUr" ""id "rd (Table 27' l) such as bitter
; t;;il; re"^ like allspice and ginger and, ftnally, essential oils i'intrr,ro, N. D,, Food Flaooring Processes, Noyes, Park Ridge, N J , 1976'
i.*on. Somelof these adJitives are permitted to be used freely, and others in Poucher, W. A.: Perfumes, Coimetics ond Soaps, vol II, 8th ed , Wiley, New York, 1974'
"f-.ra
limited
"rd
amounts,
pruth, J. S.: Sltlces aid Condiments, ChemistrE, Mtuobiology, Technology, Academic, New York, 1980.
t Contrary to Root, W. led.), He&s and Spices, Mccraw-Hill, New York, 1980'
ih" fpl is conducting an on-going review of the GRAS list of substarrces'
products is not com- Telanishi, R.-and R. A. Flath (eds.): Flat.,orResearch,Rebent Adoances, Marcel Dekker, New York, ]981.
p";;;r- ;d*"r, governniental ,"gul"iio, concerning safety in food
Toirey, S.; Fragrances and Flavors, Noyes, Park Ridge, N'J., 198.0'
pt"iety bi"t"d on ihe side of the food industry'
is useful in gaining perspective on the use o{ food additives
to realize that the average
It
t! p"' year, and of that only 63 kg are food additives Of the
p"rr* of food
"orrr,*"Joso and dextrose which are all normal'
63 kg, 58.5 kg are compor"d of "'g'i, salt, corn syrup'
to adjust the acidity account for 4 kg'
.","i"f t*arl* Leavening agents Jr substances used
olr [g of other additives. These are divided among about r80o dif-
which leaves only about
food and add greatly
ferent substances. Food Jir,ii* pl"V an invaluable role in
preserving
and For any new food additive the
i"'iu *.r"r, stability, flauor, abundance, appearance'
documented
of a Food Additive Petition (FAP) which must contain
FDA requires lubmission
into.r.,"iio., on safety,'declaration of intended use(s), efficacy at specific levels in the food
;;;;, ;;"rfacturing detaiis including intermediates, and an environmental impact state-
just to obtain FDA approval'
ment. It has been estimated that it carieasily cost $I million
igt *rt, new products have been approved in the last 20
;;;;" oiit i, t less than a dozen
years, but the FDA is currently
vears. Most of the additires used have been apf.or"d for
in requiring the retesting of rnany of them'
"rrg"g"d
NATUVAL ACCESSORY CHEMTCALS. Foodstuffs contain small
amounts of accessory cherr'li-
Carbohydrates
i.,"i,rding vitamins (Chap: 40), chelating agents, and.natural antioxidants'
""ir, starches, dextrins (Chap. 3b), celluloses, and !ums. Proteins are com-
consist of various sugars,
stearic acids'
p.*J
-Natural .i"*i"o acid"s. Shortenings contain esters of palmitic, oleic, linoieic, andsubstances that
oI no known nutritive value' as well as
foodstuffs contain substinces
if in turg"i than are normally used; for example, coffee"and tea
.r"-r,".-rrr taken
".ounts Even small amounts of arsenic
contain caffeine, *hose pha'rmacological effect is well known,
and other toxic metals are found in food'
potatoes contain so much solanine (a deadly poiSon) that if the amount consumed by the
average person in a year was concentrated into a single dose,
it would be. sufficient to kill a
but it suffilient to realize that "natural" foods are
horse. Thelist could be extended greatly, is
and
;;;";;,t;;;; safer tha"n properly prepared food containing carefullv tested
"r
controlled additives.

SELECTED REFERENCES

Aooell. L.: and Flarsors, Novox' Whiting N f

Co$tttctircE, Fiagyances,
dtil"il",ud M. e.;rJ 6. E. Inglett: Fhoor o! Foods ond Birserages, Aeademic' New York, I97r
]
t;;d;a, W.:E. and f. A. Rogers,lr.: The Frogrance and.Flaoor Industry, Dorland, Mendham,
1977.
E.t i". N. L..M: Plant Pfgments, Flaoon and Textures, Academic, New York' 1979'
f*iiriu iiiliurr*'iii'iiitier"itxnt'zd4.'-clc press, Boca Raton, Fla.. te75.
CRC Press, Boca Raton' FIa" 1973'
i'"J"; f s. i"a;, noidfuk of F-ood
dddtttoes, za
"a"
alf lt's Naturai, How Good Is It? Food Eng.54 (3) 7 (1982)'