FLAVOUR AND FRAGRANCE JOURNAL, VOL. 1.

9-15 (1985)

The Application of Carnation in Perfumery

Danute Pajaujis Anonis
9 8 4 1 64th Road, Forest Hills, New York 11374. U.S.A.

Carnation, Dianthus caryophyllus L., which originated in the Mediterranean countries, holds an important place in
perfumery. Southern France, Italy, Egypt, and Kenya are now the main sources of carnation flowers for perfumery
use. The flowers are extracted with volatile solvents, yielding carnation concrete, which on treatment with alcohol,
gives carnation absolute.
Until the 1930s, only a few components of steam-distilled carnation oil were known. Carnation was not the
subject of further research until in the 1980s over a hundred components were revealed in the steam-distilled oil
and in Egyptian carnation absolute. The difference in chemical compositions of absolutes and steam-distilled oils,
obtained from flowers cultivated in Kenya, Egypt and in South of France was also shown. Carnation absolute is
very expensive, therefore synthetic carnation compounds have been developed, the main components being
eugenol and its derivatives combined with salicylates, benzoates and rose components. Few illustrative conven-
tional carnation formulas are shown. More recent carnation compounds include newer aromatics, amongst which
cis-hex-3-enyl esters are important. At the beginning of this century, pure concentrated carnation essence were
used as perfumes. Later, carnation absolute served as modifier in many perfume compositions.
Early carnation fragrances were based mostly on a few natural perfume materials, including carnation absolute.
Later, a few essential oils and aromatics were added as they became available. Examples of carnation perfumes are
given. In the late 1930s, alcohol-free perfume concentrates were developed, among them carnation. Spicy notes
are appealing to men, and many men's fragrances, ranging from the early to the sophisticated modern
formulations contain carnation notes. Carnation perfumes have been used in brilliantines, hair oils, talcum
powders and soaps. Apart from soap perfumes, they contained small amounts of carnation absolute. Carnation
fragrances are still used to perfume colored soaps. In modern cosmetic perfumes, carnation is mostly used as a
modifying component of a fragrance to give a warm spicy floral note. Carnation absolute is used today only in de
luxe fragrances, because of its high price.' Synthetic carnation compounds or their components have replaced the
absolute in less expensive perfumes. Efforts are being made to introduce a lower priced carnation ingredient,
cultivated and produced in Kenya, to encourage its use in perfumery. The carnation odor is important in both
women's and men's fragrances, and it will remain an indispensable component of fragrances created in the future.

K E Y WORDS Carnation oil Chemical composition Synthetic compounds Perfumery

INTRODUCTION METHOD OF PRODUCTION, YIELD, AND

TYPE OF OIL
Spicy notes hold an important place in perfumery,
and carnation is among them. As in food, spicy
odors add warm, exotic notes to an otherwise Carnation flowers for perfumery use are
ordinary perfume composition. extracted principally in Grasse, France. Volatile
solvents are used, yielding a concrete and abso-
lute of carnation, the latter not containing any
BOTANICAL ORIGIN insoluble waxes.
On extraction with petroleum ether, the flow-
Dianthus caryophyffusL. (fam. Caryophyllaceae) ers normally yield 0.23 to 0.29% of concrete
originated in Mediterranean countries, but it is (maximum, 0.33%). When the concrete is
now cultivated in many other countries, primarily extruded with alcohol it yields between 9-1296 of
for the flower trade. the absolute.' The absolute has a peppery carna-
O 8 8 2 - 5 7 3 3 / 8 5 / 0 1 OOO!l-O7$@ l .OO Received 29 February I984
%I 1985 by John Wiley & Sons, Ltd
10 DANUTE PAJAUJIS ANONIS

tion odor, the concrete is less peppery and has a which 2-ethylhexanol was specifically men-
more green leafy odor. tioned.
At the beginning of the century up to 200 metric 4. The other oxygenated compounds, i.e. car-
tons of carnation flowers were processed annually bony1 derivatives, esters, ethers, were a com-
in Grasse, but in the 1950s only a few tons were plex mixture in which jasmone, methyl jasmo-
extracted. The production has declined steadily nate and a number of cis-hex-3-enyl esters
since then.* were identified. A special mention was made
Lately, carnation flowers have been cultivated of cis-hex-3-enyl trans-hex-2-enoate (different
in Egypt and Kenya, the latter being developed to from cis-hex-3-enyl cis-hex-3-enoate identified
obtain a more cost effective product which could previously in gardenia absolute). Also, four
bring about a renewed interest in its use. A con- pairs of alpha, beta-ethylenic ketones, present
crete is prepared by hexane extraction, the yield in trace amounts, were identified.
being about 0.25%.3Today, the combined annual The presence of cis-hex-3-enyl benzyl ether
industrial production of carnation flowers for (16.5%) and dibenzyl ether (4.5%) in this frac-
processing amounts to 50-70 t o m 4 tion were considered by the researchers as
Although carnation absolute is still produced, artifacts, and their formation remained unex-
synthetic carnation compounds based on eugenol plained.
and its derivatives, modified with nitriles and A partial list of constituents identified in the
other new aromatics, are mostly used in perfum- steam distilled oil with indicated relative percen-
ery. tages is given in Table 1.

CHEMICAL COMPOSITION Table 1. Partial constituents of steam

distilled carnation oil6

By 1930, the following components were iden- Constituents %

tified in the steam-distilled carnation oil:
Phenols
eugenol 20.8
Eugenol 30%
Phenylethyl alcohol 7% Alcohols
benzyl alcohol 0.53
Benzyl benzoate 40%
cis-hex-3-enol 0.60
Benzyl salicylate 5% linalool 2.25
Methyl salicylate 1% alpha terpineol 0.31

Aldehydes and ketones

There was little further research until the 1980s benzaldeh yde 0.92
when carnation absolute and a steam-distilled oil, jasmone 0.38
both obtained from the same Egyptian carnation
concrete, were analyzed.6Then, many, new com- Esters
benzyl benzoate 11.80
ponents were identified. The chromatogram of
the steam-distilled oil showed that most con- benzyl salicylate 1S O
stituents are eluted before the eugenol peak,
whereas in the case of the absolute, the important cis-hex-3-en yl benzoate 1.15
constituents are mainly eluted after the eugenol methyl jasmonate co.01
peak.
Among the groups of compounds isolated in
the analysis of the steam distilled oil, were:
1. The hydrocarbons, which represented 27% of In the analysis the absolute was divided into
the oil. two fractions (after removal of the major part of
2. The aldehydes were less than 1%.The unusual the free acids): non-polar (hydrocarbons) and
presence of 2-ethylhexanol was noted. polar (oxygenated and other compounds).
3. The oxygenated fraction (free of phenols and The hydrocarbons, representing over 20% of
acids) contained 29% of alcohols, among the absolute, consisted mostly of linear olefins,
 APPLICATION OF CARNATION IN PERFUMERY 11

Table 2. Partial constituentsof absolute cis-hex-3-enyl tiglate,

carnation6 cis-hex-3-enyl isovalerate,
Constituents %
cis-hex-3-enyl octanoate,
cis-hex-3-enyl nonanoate.
Ethers and Phenol., A total of 110 constituents were identified, of
eugenol 3.6
which 95 had not been reported before.
Alcohols In another recent study,7 carnation absolutes
benzyl alcohol 0.08
cis-hex-3-en01
obtained from carnation concretes Pays, Egyptian
0.01
linalool 0.02 and Kenyan and the steam distilled oils were
alpha-terpineol 0.03 analyzed and their chemical compositions were
Aldehydes and ketones
compared. It was found that both the steam distil-
benzaldehyde 0.01 led oils and the absolutes from Pays and Kenya
jasmone 0.56 were similar in chemical composition, while the
Esters Egyptian oil and absolute showed a greater dif-
benzyl benzoate 14.6 ference, the latter was also of a lighter colour:
yellow-green versus the dark green colour of both
benzyl salicylate 3.9 Pays and Kenya absolutes.
cis-hex-3-enyl benzoate 0.54 The concrete Pays yielded 16% of the absolute,
the Kenyan 14%, and the Egyptian 11%.7
methyl jasmonate co.01 The steam distilled oil obtained from the Egyp-
tian absolute amounted to 13%,as compared to
methyl linoleate 2.25
3% and 6% respectively from the Kenyan and
Pays.7
The main difference in the chemical composi-
the three main ones being tricosene, pentacosene tion of the Egyptian oil was a higher content of
and heptacosene. eugenol and lower percentages of citronellol,
The oxygenated fraction (excluding eugenol hexyl and hexenyl benzoates, as shown below in
and benzyl benzoate), contained aliphatic acid- Table 3:
methyl esters, the main one being methyl linole-
ate.
Among esters, the presence of benzyl salicy- Table 3. Carnation steam distilled oil7
late, known from earlier research, was confirmed.
Kenyan Pays Egyptian
Traces of hexyl salicylate and cis-hex-3-enyl Components % % %
salicylate were identified, the latter being novel.
No methyl salicylate, identified earlier,’ was Citronellol 2.2 2.7 0.2
found in either the absolute or the steam distilled Hexyl benzoate 3.2 4.1 c 0.1
oil. Hexenyl benzoate 11.4 10.1 3.0
Eugenol 2.3 3.8 12.5
A partial list of constituents identified in the Benzyl benzoate 30.0 32.0 38.0
absolute with indicated relative percentages is
given in Table 2.
Other aromatics, identified but not quantified.6 Because of the low amount of eugenol (the
include: principal component of synthetic carnation)
cis- and trans-linalol oxides, found in the absolutes by analytical chromato-
2-methoxyphenol, graphical analysis, the three absolutes were ana-
2-ethylhexan-1-01, lyzed by high pressure liquid chromatography. It
2-ethylhexanol, was found that the relative percentages of
hexyl benzoate, eugenol in all three absolutes were five times
hexyl salicylate, higher than those found previously. The relative
phenethyl tiglate, percentages of benzoates were close in both
phenethyl octanoate, analyses.
cis-hex-3-enyl trans-hex-2-enoate, The above results are illustrated below by data
neryl hexanoate, given in Table 4.
12 DANUTE PAJAUJIS ANONIS

Table 4. Composition of Carnation absolute'

Kenyan Pays Egyptian

% % %
Components HPLC Calculated' HPLC Calculated* HPLC Calculated*

Eugenol 0.45 0.06 0.95 0.2 8.6 1.7

Benzyl benzoate 1.8 0.9 2.1 1.8 5.5 5.0
Hexenyl benzoate 0.3 0.4 0.4 0.6 t 0.4
Hexvl benzoate
~~
+ 0.1 + 0.2 - 0.01

'Calculated from data obtained by analytical chromatographic analysis of corresponding oils.

+The benzoate amount could not be calculated because of interfering peaks.

The content of eugenol in all three steam distil- SYNTHETIC COMPOUNDS

led oils were comparable in both analyses.
The above study thus confirmed that the steam Eugenol and its derivatives combined with salicy-
distillation was not complete, and that it does not lates, benzoates and rose alcohols constitute the
give the true value of the amount of eugenol in base of conventional synthetic carnation com-
carnation absolute. pounds. Amy1 oxy isoeugenol has been also used.
Comparing results of earlier research work on The salicylates round out the harshness, and also
carnation with those of recent research work, we act as fixatives. Among other fixatives used are
find some differences, especially in the percen- heliotropin, musk ketone, vanillin and the
tages of eugenol in the steam-distilled oil, as illus- resinoids benzoin, civet, styrax and tolu. Jasmin,
trated in Table 5. lilac, lily of the valley and violet components con-
tribute floral odor characteristics. Phenylacetal-
Table 5. Carnation steam-distilled oil dehyde, hydratropic aldehyde, dimethyl benzyl
carbinyl acetate, anisic aldehyde, phenylpropyl
From From From aldehyde, guaiacwood acetate and aldehydes
absolute absolute concrete C-10, C-ll(enic), C-l2(MNA) and C-16 may be
German5 Egyptian' Egyptian6
Components % % % used as modifiers. Of the natural modifying ma-
terials, geranium oil, petitgrain oil, and jasmin
EugenoI 30 12.5 20.8 absolute are worthy of mention. Among trace
Benzyl benzoate 40 38 11.8 ingredients are basil oil, black pepper oil, carrot
Citronellol - 0.2 -
Phenyl ethyl alcohol 7 - * seed oil, estragon oil, nutmeg oil and terpeneless
~~ ~~
pimento oil. Clarly sage oil is recommended' to
'Percentage not given. tone down the pepper note; hydroxycitronellal
has the same effect.
The results of two recent studies reveal varia- Carnation shares common ingredients with
tion in percentages of both eugenol and benzyl cloves and cinnamon (eugenol), clover (amyl
benzoate in carnation absolute, as shown in salicylate), jasmin and Ylang ylang (benzyl ace-
Table 6. tate), rose (phenethyl alcohol, nerol, rhodinol),
and to a smaller extent, with lilac and lily of the
Table 6. Carnation absolute Egyptian valley (hydroxycitronellal, cinnamic alcohol),
tuberose (methyl salicylate) and violet (ionones).
Ref. 6 Ref. 7 Carnation, orange and jasmin form an osmi-
% % a l l y balanced odour complex. The odour of car-
Components HPLC Calculated
nation blends well with woody and leather notes.
Eugenol 3.6' 8.6 1.7 Interesting accorded notes can be achieved in
B e m l benzoate 14.6 5.5 5.0 combining carnation with tuberose and narcissus.
Let us take a look at few illustrative conven-
*Recorded by integrator. tional carnation formulas.
 APPLICATION OF CARNATION IN PERFUMERY 13

An example of carnation base: oxide, cis-hex-3-eno1, cis-hex-3-ena1, cis-hex-3-

enyl benzoate, cis-hex-3-enyl salicylate, cis-hex-
3-enyl tiglate, and cis-hex-3-enyl isovalerate are
Carnation Base B-9 available.
750 Eugenol
100 Amy1 salicylate
New patents have been issued on nitrile, cyclo-
hexenone, and pyran derivatives, e.g. dimethyl
60 Phenyl ethyl alcohol
hepten~nitriles,~of a spic odor tonality,
40 Nerol
30 Phenylacetaldehyde (50% in
3-phenylcyclohex-2-en-l-one,'8 possessing a
warm spicy odor (useful for cosmetics, soaps, and
phenyethyl alcohol) deter ents); and 2,4-disubstituted pyran deriva-
20 Benzyl benzoate
tives!' having spicy, and herbal notes.
15 Alpha ionone
5 Black pepper oil.
IMCOMPATIBILITY
An example of a synthetic carnation:
The principal components of carnation com-
Carnation C-3 pounds, i.e. eugenol and isoeugenol oxidise easily
310 Eugenol in air and change both in odour and colour. They
110 Phenethyl alcohol can be stabilized to some extent with benzyl
50 Benzyl salicylate salicylate. The methyl ether and acetyl ester of
50 Jasmin synthetic eugenol and isoeugenol are more stable in alkali
40 Ylang ylang oil than the free Phenols. Musk xylol and vanillin will
35 Cinnamic alcohol also contribute to the discoloration. Phenethyl
35 Heliotropin alcohol and vanillin tend to associate with the
35 Methyl isoeugenol protein substrate," and the amounts of these
35 Hydroxycitronellal aromatics should be limited in carnation com-
30 Alpha ionone pounds used in cosmetic preparations containing
30 Nerol proteins.
20 Musk ketone
15 Ethyl vanillin
5 Methyl salicylate SENSITIZATION
5 Civet synthetic
5 Aldehyde C-ll(enic) 10%. Bromstyrol has been completely eliminated
because of its harmful dermatological effect.
Isoeugenol, cinnamic alcohol, and cassia oil are
More recent carnation compounds may include used only in limited amounts. Phenylacetal-
cinnamyl nitrile, (replacing cinnamic aldehyde) dehyde and cinnamic aldehyde are used in con-
geranoxide (a spicy odor tonality with ginger and junction with quenchers, and only specially pro-
fenugreek overtones), cinnamyl acetate (a bal- cessed styrax is used in carnation compounds.
samic sweet odor, replacing in part cinnamic
alcohol). Hydroxycitronellal is being replaced by
cyclamen aldehyde derivatives or other hydroxy- APPLICATION
citronella1 substitutes. Newer aromatics, such as
rose oxides, damascones, damascenones, methyl At the beginning of the century, pure natural con-
dihydro jasmonate, the lactone of cis-jasmone centrated carnation essences were offered along
and jasmone may be used per se or in synthetic side other flower oils as fragrances.
rose and jasmin compounds, contributing the Later, carnation absolute was used up to 15%
floral odor tonality. Civetone may be used as part in synthetic carnation, and in smaller amounts in
of a synthetic civet, and a variety of new synthetic sweet pea, clover, fougere and leather composi-
musks may be used to advantage as fixatives. tions.
Of the newly identified aromatics in carnation Early carnation fragrances were built on rose,
absolute and in the hydrodistillation oil,6linalool tuberose, orange flower, and natural cassie flower
14 DANUTE PAJAUJIS ANONIS

extracts. Essential oils of bergamot and ylang, as the above. Small amounts of carnation absolute
well as small amounts of rose Otto, neroli, carna- or concrete have been added to carnation com-
tion, jasmin, and tuberose absolutes were added pounds used in cream, talcum powder, hair oils
as modifying roles to such compositions. Later, and brilliantines.
several aromatics were included, i.e. In soap perfumes, benzyl isoeugenol, vanillin,
linalol,methyl isoeugenol, isoeugenol, musk heliotropin, musk xylol, clove resinoid, civet
ketone, aldehyde C-8, and alcohol and aldehyde synthetic and resinoids benzoin and tolu are used
C-9. Civet and castoreum, benzoin, ambrette as fixatives. Bromstyrol and amyl oxy isoeugenol
seed, adn vanilla bean infusions were used as fixa- are ingredients which perform well in carnation
tives. l 3 soap fragrances. The carnation odor is very long
Before the 1940s, innovative alcohol-free per- lasting, but suih ingredients can only be used in
fume concentrates were developed in Germany. dark colored soaps because they cause discolora-
The perfume oils were dissolved in various sol- tion is light coloured soaps.
vents, i.e. diethyl phthalate, castor oil, etc. A Today, modern carnation compounds are used
synthetic carnation perfume was among other among other single florals as soap fragrances,
floral fragrances offered. l4 especially in Europe. In cosmetic fragrances, car-
Of the early carnation perfumes, Oeillet du nation is an essential note of many popular com-
Roy was a fragrance of notable quality. Among mercial creations.
other established fragrances containing varying
amounts of carnation notes are: Origan, Bellod-
gia, Cashmere Bouquet, Blue Grass, Chantilly, CONCLUSION
L‘Air du Temps, Interdit, Mitsouko, Nuit de
Noel, Moment Supreme, Tigress, and Tabu. Synthetic carnation compounds have replaced the
Some of the more recent fragrances containing expensive carnation absolute and concrete in all
carnation or its components are: Norell, Oscar de but the de luxe fragrances. Recently, efforts are
la Renta, Missoni, Opium, Gauloise, Grain de being made to introduce a less expensive carna-
Sable, K de Krizia, Nipon, and Champagne. tion, cultivated and produced in Kenya, the abso-
Carnation has been used as a single floral lute of which is similar in chemical composition to
cologne, complements the conventional range of that of the Pays absolute. This may encourage the
Florida, Cananga, and Portugal types of cologne. use of carnation absolute in a wider range of
The concentration of the perfume oil” in such fragrances.
colognes varied from 2-696, the average being Synthetic carnation compounds are being mod-
3%. ernized by the addition of newly discovered
Today carnation is still being offered among aromatics, and by the elimination of incompatible
other floral scents to be used in sprays, toilet or dermatologically unacceptable components of
water, or perfume. the older, cruder extracts.
The spicy notes, including carnation have The carnation odor is popular with both sexes,
always had an appeal to men. Back in 190716 and it will remain an integral part of both
Oeillet du Roy, a women’s fragrance, was well women’s and men’s fragrances of the future.
accepted by men. The longevity of Old Spice
speaks for itself. The spicy note remains part of REFERENCES
the sophisticated men’s fragrances; containing
carnation or its components are: Stetson, Calvin 1 . Naves and Mazuyer, Les Parfirm Naturels, p. 250, Pans
for Men, and Anteus. (1939).
Carnation perfume compounds have been used 2. E. Guenther, The Essenrial oils, Vol. 5 , p. 413, Van Nos-
in talcum powder, hair oils, brilliantines, and trand, New York (1952).
3. M. Derbessy, J. C. Bayle, M. Remy and H. H. Peter,
soap. Paper 130.8rh Int. Congr. ofEssent. oils, Cannes, France
In carnation for talcum powder, coumarin, (1983).
heliotropin, synthetic masks, benzyl isoeugenol, 4 . Personal Communicarion, P. Robertet Inc. (1983).
methyl isoeugenol, isoeugenol, isobutyl benzoate, 5 . W. Treff and H. Wittrisch, 1. Prakr. Chem., 122, 232
(1929).
and isobutyl salicylate serve as fixatives. 6 . P. Buil, J. Garner0 and D. Joulain, Paper 555, 9rh Inr.
In hair oils which require stronger fixation, Congr. Essenr. Oils, Singapore (1983).
benzoin infusions have been used in addition to 7 . M. Derbessy et al., ibid.
 APPLICATION OF CARNATION IN PERFUMERY 15

8. R. Cerbelaud, Formulaire de Parfumerie, p. 159, Ed. 12. S. Lemberg, Amer. Cosmet. Perf., 6 , 38 (1972).
Opera, Paris (1 95 1). 13. H. Fouquet, La technique Moderne et les Formules de la
9. U.S. patent No. 4, 277, 377, (E.P. 17,396) assigned to Parfitmerie, p. 195, Librairie Polytechnique Ch.
Bush Boake AUen Limited, England (1981), Perf 13 BCranger, Paris (1951).
Fhvorisr, 2, 64 (1982). 14. Ibid., pp. 135, 142.
10. U.S.patent No. 4, 255, 292, assigned to Firmenich SA, 15. 0.Gerhardt,Dar Komponieren in der Parfumerie, p. 220,
Switzerland (1981), Chem. Abs., 93, 191915 (1980). Akademische Verlagsgesellschaft, Leipzig (1931).
1 1 . U.S. patent No. 4, 293, 244, assigned to BASF 16. M. Billot, Amer. Perf. Cosmer., 4, 52 (1966).
Aktiengesellschaft,Germany (1981), Perf: & Ruvorisr, 6,
50 (1981/82).