The Application of Carnation in Perfumery

FLAVOUR AND FRAGRANCE JOURNAL, VOL. 1. 9-15 (1985) The Application of Carnation in Perfumery Danute Pajaujis Anonis 9841 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 conventional 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. KEY WORDS Carnation oil Chemical composition Synthetic compounds Perfumery INTRODUCTION 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 ordinary perfume composition. BOTANICAL ORIGIN Dianthus caryophyffus L. (fam. Caryophyllaceae) originated in Mediterranean countries, but it is now cultivated in many other countries, primarily for the flower trade. O882-5733/85/0 1 OOO!l-O7$@ l.oo %I 1985 by John Wiley & Sons, Ltd METHOD OF PRODUCTION, YIELD, AND TYPE OF OIL Carnation flowers for perfumery use are extracted principally in Grasse, France. Volatile solvents are used, yielding a concrete and absolute of carnation, the latter not containing any insoluble waxes. On extraction with petroleum ether, the flowers normally yield 0.23 to 0.29% of concrete (maximum, 0.33%). When the concrete is extruded with alcohol it yields between 9-1296 of the absolute.' The absolute has a peppery carna- Received 29 February I984

10 DANUTE PAJAUJIS ANONIS tion odor, the concrete is less peppery and has a more green leafy odor. At the beginning of the century up to 200 metric tons of carnation flowers were processed annually in Grasse, but in the 1950s only a few tons were extracted. The production has declined steadily since then.* Lately, carnation flowers have been cultivated in Egypt and Kenya, the latter being developed to obtain a more cost effective product which could bring about a renewed interest in its use. A concrete is prepared by hexane extraction, the yield being about 0.25%.3 Today, the combined annual industrial production of carnation flowers for processing amounts to 50-70 tom4 Although carnation absolute is still produced, synthetic carnation compounds based on eugenol and its derivatives, modified with nitriles and other new aromatics, are mostly used in perfumery. which 2-ethylhexanol was specifically mentioned. 4. The other oxygenated compounds, i.e. carbony1 derivatives, esters, ethers, were a complex mixture in which jasmone, methyl jasmonate and a number of cis-hex-3-enyl esters were identified. A special mention was made of cis-hex-3-enyl trans-hex-2-enoate (different from cis-hex-3-enyl cis-hex-3-enoate identified previously in gardenia absolute). Also, four pairs of alpha, beta-ethylenic ketones, present in trace amounts, were identified. The presence of cis-hex-3-enyl benzyl ether (16.5%) and dibenzyl ether (4.5%) in this fraction were considered by the researchers as artifacts, and their formation remained unexplained. A partial list of constituents identified in the steam distilled oil with indicated relative percentages 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 There was little further research until the 1980s when carnation absolute and a steam-distilled oil, both obtained from the same Egyptian carnation concrete, were analyzed.6 Then, many, new components were identified. The chromatogram of the steam-distilled oil showed that most constituents are eluted before the eugenol peak, whereas in the case of the absolute, the important constituents are mainly eluted after the eugenol peak. Among the groups of compounds isolated in the analysis of the steam distilled oil, were: 1. The hydrocarbons, which represented 27% of the oil. 2. The aldehydes were less than 1%. The unusual presence of 2-ethylhexanol was noted. 3. The oxygenated fraction (free of phenols and acids) contained 29% of alcohols, among Aldehydes and ketones benzaldeh yde 0.92 jasmone 0.38 Esters benzyl benzoate 11.80 benzyl salicylate 1 S O cis- hex-3-en yl benzoate 1.15 methyl jasmonate co.01 In the analysis the absolute was divided into two fractions (after removal of the major part of the free acids): non-polar (hydrocarbons) and polar (oxygenated and other compounds). The hydrocarbons, representing over 20% of the absolute, consisted mostly of linear olefins,

APPLICATION OF CARNATION IN PERFUMERY 11 Table 2. Partial constituents of absolute carnation6 Constituents % Ethers and Phenol., eugenol Alcohols benzyl alcohol cis-hex-3-en01 linalool alpha-terpineol Aldehydes and ketones benzaldehyde jasmone Esters benzyl benzoate benzyl salicylate cis-hex-3-enyl benzoate methyl jasmonate methyl linoleate 3.6 0.08 0.01 0.02 0.03 0.01 0.56 14.6 3.9 0.54 co.01 2.25 the three main ones being tricosene, pentacosene and heptacosene. The oxygenated fraction (excluding eugenol and benzyl benzoate), contained aliphatic acidmethyl esters, the main one being methyl linoleate. Among esters, the presence of benzyl salicylate, known from earlier research, was confirmed. Traces of hexyl salicylate and cis-hex-3-enyl salicylate were identified, the latter being novel. No methyl salicylate, identified earlier, was found in either the absolute or the steam distilled oil. A partial list of constituents identified in the absolute with indicated relative percentages is given in Table 2. Other aromatics, identified but not quantified.6 include: cis- and trans-linalol oxides, 2-methoxyphenol, 2-ethylhexan-1-01, 2-et h ylhexanol, hexyl benzoate, hexyl salicylate, phenethyl tiglate, phenethyl octanoate, cis-hex-3-enyl trans-hex-2-enoate, neryl hexanoate, cis-hex-3-enyl tiglate, cis-hex-3-enyl isovalerate, cis-hex-3-enyl octanoate, cis-hex-3-enyl nonanoate. A total of 110 constituents were identified, of which 95 had not been reported before. In another recent study,7 carnation absolutes obtained from carnation concretes Pays, Egyptian and Kenyan and the steam distilled oils were analyzed and their chemical compositions were compared. It was found that both the steam distilled oils and the absolutes from Pays and Kenya were similar in chemical composition, while the Egyptian oil and absolute showed a greater difference, the latter was also of a lighter colour: yellow-green versus the dark green colour of both Pays and Kenya absolutes. The concrete Pays yielded 16% of the absolute, the Kenyan 14%, and the Egyptian 11%.7 The steam distilled oil obtained from the Egyptian absolute amounted to 13%, as compared to 3% and 6% respectively from the Kenyan and Pays.7 The main difference in the chemical composition of the Egyptian oil was a higher content of eugenol and lower percentages of citronellol, hexyl and hexenyl benzoates, as shown below in Table 3: Table 3. Carnation steam distilled oil7 Kenyan Pays Egyptian Components % % % Citronellol 2.2 2.7 0.2 Hexyl benzoate 3.2 4.1 c 0.1 Hexenyl benzoate 11.4 10.1 3.0 Eugenol 2.3 3.8 12.5 Benzyl benzoate 30.0 32.0 38.0 Because of the low amount of eugenol (the principal component of synthetic carnation) found in the absolutes by analytical chromatographical analysis, the three absolutes were analyzed by high pressure liquid chromatography. It was found that the relative percentages of eugenol in all three absolutes were five times higher than those found previously. The relative percentages of benzoates were close in both analyses. The above results are illustrated below by data 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 distilled oils were comparable in both analyses. The above study thus confirmed that the steam distillation was not complete, and that it does not give the true value of the amount of eugenol in carnation absolute. Comparing results of earlier research work on carnation with those of recent research work, we find some differences, especially in the percentages of eugenol in the steam-distilled oil, as illustrated in Table 5. Table 5. Carnation steam-distilled oil From From From absolute absolute concrete German5 Egyptian' Egyptian6 Components % % % E u g e n o I 30 12.5 20.8 Benzyl benzoate 40 38 11.8 Citronellol - 0.2 - Phenyl ethyl alcohol 7 - * 'Percentage not given. The results of two recent studies reveal variation in percentages of both eugenol and benzyl benzoate in carnation absolute, as shown in Table 6. Table 6. Carnation absolute Egyptian Ref. 6 Ref. 7 % % Components HPLC Calculated Eugenol 3.6' 8.6 1.7 Beml benzoate 14.6 5.5 5.0 *Recorded by integrator. SYNTHETIC COMPOUNDS Eugenol and its derivatives combined with salicylates, benzoates and rose alcohols constitute the base of conventional synthetic carnation compounds. Amy1 oxy isoeugenol has been also used. The salicylates round out the harshness, and also act as fixatives. Among other fixatives used are heliotropin, musk ketone, vanillin and the resinoids benzoin, civet, styrax and tolu. Jasmin, lilac, lily of the valley and violet components contribute floral odor characteristics. Phenylacetaldehyde, hydratropic aldehyde, dimethyl benzyl carbinyl acetate, anisic aldehyde, phenylpropyl aldehyde, guaiacwood acetate and aldehydes C-10, C-ll(enic), C-l2(MNA) and C-16 may be used as modifiers. Of the natural modifying materials, geranium oil, petitgrain oil, and jasmin absolute are worthy of mention. Among trace ingredients are basil oil, black pepper oil, carrot seed oil, estragon oil, nutmeg oil and terpeneless pimento oil. Clarly sage oil is recommended' to tone down the pepper note; hydroxycitronellal has the same effect. Carnation shares common ingredients with cloves and cinnamon (eugenol), clover (amyl salicylate), jasmin and Ylang ylang (benzyl acetate), rose (phenethyl alcohol, nerol, rhodinol), and to a smaller extent, with lilac and lily of the valley (hydroxycitronellal, cinnamic alcohol), tuberose (methyl salicylate) and violet (ionones). Carnation, orange and jasmin form an osmially balanced odour complex. The odour of carnation blends well with woody and leather notes. Interesting accorded notes can be achieved in combining carnation with tuberose and narcissus. Let us take a look at few illustrative conventional carnation formulas.

APPLICATION OF CARNATION IN PERFUMERY 13 An example of carnation base: Carnation Base B-9 750 Eugenol 100 Amy1 salicylate 60 Phenyl ethyl alcohol 40 Nerol 30 Phenylacetaldehyde (50% in phenyethyl alcohol) 20 Benzyl benzoate 15 Alpha ionone 5 Black pepper oil. An example of a synthetic carnation: Carnation C-3 310 Eugenol 110 Phenethyl alcohol 50 Benzyl salicylate 50 Jasmin synthetic 40 Ylang ylang oil 35 Cinnamic alcohol 35 Heliotropin 35 Methyl isoeugenol 35 Hydroxycitronellal 30 Alpha ionone 30 Nerol 20 Musk ketone 15 Ethyl vanillin 5 Methyl salicylate 5 Civet synthetic 5 Aldehyde C-ll(enic) 10%. More recent carnation compounds may include cinnamyl nitrile, (replacing cinnamic aldehyde) geranoxide (a spicy odor tonality with ginger and fenugreek overtones), cinnamyl acetate (a balsamic sweet odor, replacing in part cinnamic alcohol). Hydroxycitronellal is being replaced by cyclamen aldehyde derivatives or other hydroxycitronella1 substitutes. Newer aromatics, such as rose oxides, damascones, damascenones, methyl dihydro jasmonate, the lactone of cis-jasmone and jasmone may be used per se or in synthetic rose and jasmin compounds, contributing the floral odor tonality. Civetone may be used as part of a synthetic civet, and a variety of new synthetic musks may be used to advantage as fixatives. Of the newly identified aromatics in carnation absolute and in the hydrodistillation oil,6 linalool 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 available. New patents have been issued on nitrile, cyclohexenone, and pyran derivatives, e.g. dimethyl hepten~nitriles,~ of a spic odor tonality, 3-phenylcyclohex-2-en-l-one,'8 possessing a warm spicy odor (useful for cosmetics, soaps, and deter ents); and 2,4-disubstituted pyran derivatives!' having spicy, and herbal notes. IMCOMPATIBILITY The principal components of carnation compounds, i.e. eugenol and isoeugenol oxidise easily in air and change both in odour and colour. They can be stabilized to some extent with benzyl salicylate. The methyl ether and acetyl ester of eugenol and isoeugenol are more stable in alkali than the free Phenols. Musk xylol and vanillin will also contribute to the discoloration. Phenethyl alcohol and vanillin tend to associate with the protein substrate," and the amounts of these aromatics should be limited in carnation compounds used in cosmetic preparations containing proteins. SENSITIZATION Bromstyrol has been completely eliminated because of its harmful dermatological effect. Isoeugenol, cinnamic alcohol, and cassia oil are used only in limited amounts. Phenylacetaldehyde and cinnamic aldehyde are used in conjunction with quenchers, and only specially processed styrax is used in carnation compounds. APPLICATION At the beginning of the century, pure natural concentrated carnation essences were offered along side other flower oils as fragrances. Later, carnation absolute was used up to 15% in synthetic carnation, and in smaller amounts in sweet pea, clover, fougere and leather compositions. Early carnation fragrances were built on rose, tuberose, orange flower, and natural cassie flower

14 DANUTE PAJAUJIS ANONIS extracts. Essential oils of bergamot and ylang, as well as small amounts of rose Otto, neroli, carnation, jasmin, and tuberose absolutes were added as modifying roles to such compositions. Later, several aromatics were included, i.e. linalol,methyl isoeugenol, isoeugenol, musk ketone, aldehyde C-8, and alcohol and aldehyde C-9. Civet and castoreum, benzoin, ambrette seed, adn vanilla bean infusions were used as fixatives. l3 Before the 1940s, innovative alcohol-free perfume concentrates were developed in Germany. The perfume oils were dissolved in various solvents, i.e. diethyl phthalate, castor oil, etc. A synthetic carnation perfume was among other floral fragrances offered. l4 Of the early carnation perfumes, Oeillet du Roy was a fragrance of notable quality. Among other established fragrances containing varying amounts of carnation notes are: Origan, Bellodgia, Cashmere Bouquet, Blue Grass, Chantilly, L Air du Temps, Interdit, Mitsouko, Nuit de Noel, Moment Supreme, Tigress, and Tabu. Some of the more recent fragrances containing carnation or its components are: Norell, Oscar de la Renta, Missoni, Opium, Gauloise, Grain de Sable, K de Krizia, Nipon, and Champagne. Carnation has been used as a single floral cologne, complements the conventional range of Florida, Cananga, and Portugal types of cologne. The concentration of the perfume oil in such colognes varied from 2-696, the average being 3%. Today carnation is still being offered among other floral scents to be used in sprays, toilet water, or perfume. The spicy notes, including carnation have always had an appeal to men. Back in 190716 Oeillet du Roy, a women s fragrance, was well accepted by men. The longevity of Old Spice speaks for itself. The spicy note remains part of the sophisticated men s fragrances; containing carnation or its components are: Stetson, Calvin for Men, and Anteus. Carnation perfume compounds have been used in talcum powder, hair oils, brilliantines, and soap. In carnation for talcum powder, coumarin, heliotropin, synthetic masks, benzyl isoeugenol, methyl isoeugenol, isoeugenol, isobutyl benzoate, and isobutyl salicylate serve as fixatives. In hair oils which require stronger fixation, benzoin infusions have been used in addition to the above. Small amounts of carnation absolute or concrete have been added to carnation compounds used in cream, talcum powder, hair oils and brilliantines. In soap perfumes, benzyl isoeugenol, vanillin, heliotropin, musk xylol, clove resinoid, civet synthetic and resinoids benzoin and tolu are used as fixatives. Bromstyrol and amyl oxy isoeugenol are ingredients which perform well in carnation soap fragrances. The carnation odor is very long lasting, but suih ingredients can only be used in dark colored soaps because they cause discoloration is light coloured soaps. Today, modern carnation compounds are used among other single florals as soap fragrances, especially in Europe. In cosmetic fragrances, carnation is an essential note of many popular commercial creations. CONCLUSION Synthetic carnation compounds have replaced the expensive carnation absolute and concrete in all but the de luxe fragrances. Recently, efforts are being made to introduce a less expensive carnation, cultivated and produced in Kenya, the absolute of which is similar in chemical composition to that of the Pays absolute. This may encourage the use of carnation absolute in a wider range of fragrances. Synthetic carnation compounds are being modernized by the addition of newly discovered aromatics, and by the elimination of incompatible or dermatologically unacceptable components of the older, cruder extracts. The carnation odor is popular with both sexes, and it will remain an integral part of both women s and men s fragrances of the future. REFERENCES 1. Naves and Mazuyer, Les Parfirm Naturels, p. 250, Pans (1939). 2. E. Guenther, The Essenrial oils, Vol. 5, p. 413, Van Nostrand, New York (1952). 3. M. Derbessy, J. C. Bayle, M. Remy and H. H. Peter, Paper 130.8rh Int. Congr. ofessent. oils, Cannes, France (1983). 4. Personal Communicarion, P. Robertet Inc. (1983). 5. W. Treff and H. Wittrisch, 1. Prakr. Chem., 122, 232 (1929). 6. P. Buil, J. Garner0 and D. Joulain, Paper 555, 9rh Inr. Congr. Essenr. Oils, Singapore (1983). 7. M. Derbessy et al., ibid.

APPLICATION OF CARNATION IN PERFUMERY 15 8. R. Cerbelaud, Formulaire de Parfumerie, p. 159, Ed. Opera, Paris (1 95 1). 9. U.S. patent No. 4, 277, 377, (E.P. 17,396) assigned to Bush Boake AUen Limited, England (1981), Perf 13 Fhvorisr, 2, 64 (1982). 10. U.S. patent No. 4, 255, 292, assigned to Firmenich SA, Switzerland (1981), Chem. Abs., 93, 191915 (1980). 11. U.S. patent No. 4, 293, 244, assigned to BASF Aktiengesellschaft, Germany (1981), Perf: & Ruvorisr, 6, 50 (1981/82). 12. S. Lemberg, Amer. Cosmet. Perf., 6, 38 (1972). 13. H. Fouquet, La technique Moderne et les Formules de la Parfitmerie, p. 195, Librairie Polytechnique Ch. BCranger, Paris (1951). 14. Ibid., pp. 135, 142. 15. 0. Gerhardt, Dar Komponieren in der Parfumerie, p. 220, Akademische Verlagsgesellschaft, Leipzig (1931). 16. M. Billot, Amer. Perf. Cosmer., 4, 52 (1966).