The Holy Fragrance Ingredients - ICE

Scientific Articles Sesquiterpenoides - the holy fragrance ingredients Michael Zviely* and Arcadi Boix-Camps** Incense is an aromatic substance which is obtained from certain resinous trees and largely employed for purposes of religious worship. The word is also used to signify the smoke or perfume arising from incense when burned. In ancient times, incense was furnished by two trees, viz. the Boswellia sacra of Arabia Felix, and the Boswellia papyrifera of India. Mention is made of it in the Bible: “Why do I need the Frankincense that comes from Sheba, and the good cane from a distant country? Your burnt offerings are not acceptable, and your sacriices are not pleasant to Me”,1 and “Spikenard and Saffron, Calamus and Cinnamon, with all Frankincense trees, Michael Zviely completed his Ph.D. and Post-Doc at the Hebrew University. He then headed a research group for TAMI (ICL) for almost ten years, and then spent eleven years as Global VP for Research, Development and Science of Frutarom Ltd. After that, he worked three years in China as the CTO for Research and Development of O'Laughlin Industries Ltd. (Shanghai), a company specializing in aroma chemicals - flavor and fragrance ingredients, botanical extracts, cooling agents and UV sunscreen ingredients, followed by a period as VP for Research and Development of Virdia Inc. (HCL CleanTech Ltd.) in Israel and in the USA, on lignocellulose originated bio-materials. In parallel, he held a visiting professorship at Jiangnan University in China for five years. Today Dr. Zviely is a consultant on technology and strategy of specialty chemicals (fragrance and flavor ingredients). Myrrh and Aloes, with all the chief spices”.2 It was procured from the bark much as gum is obtained at present. To enhance the fragrance and produce a thicker smoke various foreign elements were added. These ingredients generally numbered four, but sometimes as many as thirteen, and the task of blending them in due proportion was assigned under the oldlaw ordinances to particular families. One important group of fragrance ingredients are found in incense of different origins – sesquiterpene related molecules. Sesquiterpenes are a class of terpenes that consist of three isoprene units and have the molecular formula C15H24. Sesquiterpenes may be acyclic or contain rings, including many unique combinations. Biochemical modiications such as oxidation or rearrangement produce the related sesquiterpenoids. Sesquiterpenes are found naturally in plants and insects. Frankincense is the gum or resin of the Boswellia Serrata tree, used for making perfume and incense. The Hebrew word for it is lavonah ‫לבונה‬, which means “white,” referring to the gum’s color. The essential oil of frankincense is produced by steam distillation of the tree resin. The oil’s chemical components are 75% monoterpenes, sesquiterpenes, monoterpenols, sesquiterpenols, and ketones. It has a good balsamic and sweet fragrance. Some Frankincense characteristic sesquiterpenoids are shown below: Name of Ingredient Structure Organoleptic Characteristics Sweet, green, herbal, fruity, tropical, minty d-Viridiflorol Arcadi Boix-Camps began his career as a perfumer at Firmenich, the 2nd biggest fragrance and flavor company, and for the last 23 years he is the president and master perfumer of Auram International Co., Ltd., a modern company enjoying a world respected technology active in high level creative fragrances both for functional and fine toiletries, sweet flavors and savory flavors. Auram is also top supplier of agarwood oils from different origins being the largest producer in the world and produces its own essential oils mostly used in house to make specialties. Arcadi is an author of many publications on perfumery and wrote several books, e.g. “Perfumery Techniques in Evolution” providing a constructive and open analysis of new perfumery materials and a profound knowledge in the use of perfumery materials in both new and traditional formulas. OH 1S-cis-Calamenene * ** Herbal, spicy CIC; mzviely@cathay-israel-chemistry.com Auram International Co., Ltd.; www.auraminternational.com; aboix@ auraminternational.com Issue 1, September 2015, Tishrei 5776 The Israel Chemist and Engineer 27 Scientific Articles Myrrh comes from a small thorny tree. Commiphora myrrha, is the most species rich genus of lowering plants in the frankincense and myrrh family, Burseraceae was cultivated in ancient times in the Arabian Peninsula. The grower made a small cut in the bark, where the resin would leak out. It was then collected and stored for about three months until it hardened into fragrant globules. Myrrh was used raw or crushed and mixed with oil to make a perfume. Myrrh oil is steam distilled directly from the myrrh resin. Its aroma is woody, earthy and a bit balsamic. Myrrh is occasionally used as lavoring agents. Somalia and Ethiopia are by far the largest producers of Myrrh.3 Some Myrrh characteristic sesquiterpenoids are shown below: Name of Ingredient Structure Organoleptic Characteristics O Typical myrrh, balsamic, woody, musty Furanoedusma1,3-diene Name of Structure Ingredient α-Santalol Typical myrrh, balsamic, woody, musty Lindestrene Dihydropyrocurzerenone O A resinous myrrh odor, best represents the odor of myrrh by itself OH OH β-Santalol Structure 28 The Israel Chemist and Engineer Typical sandalwood odor, with powerful woody, milky and urinous tonalities6 Organoleptic Characteristics O 4S,5R-Dihydrokaranone Strong woody, slightly camphoraceous, fumigating note, remarkable, intense, woody8a,b O Woody, amberlike, elegant8a,c 4S,5R-Karanone O One of the oldest incense materials, Sandalwood, has been in use for at least 4,000 years. The sandal tree, botanically known as Santalum album belongs to the family Santalaceae. The sandal tree grows almost exclusively in the forests of Karnataka, followed by Tamil Nadu, Kerala and Andhra Pradesh, Timor Islands of Indonesia etc. The Sandalwood appears in the Bible as one of the Temple building materials – Almog ‫אלמוג‬: “Also Hiram’s ships that delivered gold from Ophir, brought from Ophir a huge quantity of Almog-wood and precious stones”.4 Sandalwood oil mainly consists of a number of closely related sesquiterpenoids. α-Santalol and β-santalol amount to more than 90% of the oil, β-santalol being the most important character impact compound. Some Sandalwood characteristic sesquiterpenoides are shown in the following table; A relatively weak, slightly woody odor reminiscent of α-cedrene5 Agarwood is the resinous heartwood of the Aquilaria tree, a genus belonging taxonomically to the Thymelaeaceae. The essential oil is a highly demanded ingredient in ine perfumery for its warm, unique balsamic notes with sandalwood– ambergris tonalities.7 In this review7 Regula Neff describes a group of sesquiterpenoides with warm, woody characteristic odor,8a which are the heart constituents of agarwood volatiles, some of them are shown below: Name of Ingredient O Organoleptic Characteristics Eremophila9,11-dien-8-one Sweet, woody, like dihydrokaranone, important oriental, fumigating character9 Bursera graveolens is a deciduous tree of the Burseraceae family that is distributed from Mexico to Peru. Its woody material has a strong characteristic spicy, sweet and balsamic odor, and is used as incense in churches where it is called “Palo Santo”. Palo Santo oil was used during the time of the Incas for its reputed spiritual purifying properties. Many members of the Burseraceae family produce a strong fragrance, demonstrated by the use of resin of plants from the Boswellia genus historically as a prominent raw material in the production of frankincense, and the usage of the resin of Commiphora molmol and closely related species as myrrh.10 Issue 1, September 2015, Tishrei 5776 Scientific Articles The following four sesquiterpenoids were isolated from Burseragra veolens: OH OH (-)-Juneol Dihydrojuneol O OH 6b-Hydroxy-4(15)eudesmen-1-one O OH 6β-Hydroxy-eudesman-4-one All four have a characteristic weak sweet, woody and herbal odor. The sesquiterpenoid molecules described above are a part of this important F&F natural ingredients, e.g. valencene,11 nootkatone,12 α- and β-vetivones and khusimone13 discussed elsewhere. There seems to be a relation between sesquiterpenoids and essential oils used for religious ceremonies. In the former short review discussing sesquiterpenoids, naming them the holy fragrance ingredients, we presented Frankincense, Myrrh, Sandalwood, Agarwood and Palo Santo.a In this part, several different Agarwood oils and ingredients will be discussed more deeply, mostly their sesquiterpenoid aroma molecules. The Agarwood species studied herein are Aquillaria Agallocha, A. Crassna, A. Baillonii, A. Beccariana, A. Malaccencis, A. Microcarpa, A. Subintegra, A. Banaensis, A. Rugosa and A. Yunnanensis. These agarwood oils smell extremely different on their top notes, namely coriaceous, animal, fecal, fruity, extremely leathery (being the most leathery those coming from Papua New Guinea and Indonesia’s Irian Jaya regions, which are called Jayapura and Mereke), cheesy, phenolic but when evaporating in the skin after 7 to 8 hours, all of them change to create the most noble, extraordinary, unexpected, surprising, amazing and astonishing woody note that has existed in the world. All of these oils converge-whatever the quality - to the same precious woody note. Studies have been done to understand the reason why and the answer seems mostly to derive amongst the important sesquiterpenoids described herein. The dry down became all the same. Many of the molecules found in Agarwood oils were smelled, from those simple like benzyl acetone, furfural, frambinone methyl ether, p-cresol, furfuryl alcohol, creosol, styrene, p-vinyl anisole, etc., molecules which are not important at all. some olfactory important acid molecules as butyric, 3-methylvalerianic, caproic, caprilic, cyclohexanoic etc., and those believed to be really “keys” in the fabulous smell sought for a millennium and being the favorite smell of Asian aristocrats in Vietnam, China, Japan, Thailand or the Indian Maharajas. It seems that the top note differences in the oils are created by unimportant ingredients while the “treasure” is in the ingredients almost nobody knows. Why do so many different oils have such a different top note, very often unpleasant, and suddenly its odor changes to impart the extraordinary woody note that is so resinous, fragrant, radiant and delicate. The oils which are fecal, cheesy are less preferred by some of the perfumers. These are mostly the cheesy ones (Boyas from India, Bangla Desh, Laos) or the oils ex A. Agallocha or A. Khasiana. The more accepted oils are from Malaysia, Indonesia, Papua New Guinea, and those from Thailand (Prachinbury ex A. Subintegra, Tratex A. Crassna and those from Cambodia ex A. Baillonii and A. Crassna too (called in the market KohKhong). These seem to be the best Agarwood oils. Why do all these oils become so woody and treasure the best smell in the world on its dry down? It is very risky to reply but there are some “key” ingredients than make the miracle as shown below: One of the best aroma molecules, being powerfully woody, resinous, timbered extraordinarily diffusive and not easy to forget once known and smelled. This seems one of the best woody chemicals existing. The synthesis of (+)-(4αS,5R)Dihydrokaranone is described (+)-(4αS,5R)-Dihydrokaranone below. O H Its smell is very strong, as the previous one extremely long lasting, with orris sub notes, clean, radiant, diffusive, bright, woody ambery, smelling a bit of Ambrocenide, Ambrostar, dextro Nor Limbanol, Ambermax, Cachalox, Z-11 and Limbanol whose greatness is to make feel harmony. O O O (-)-Guaia-1(10),11-dien-15,2-olide OH A storm of the noblest woods, a moving smell, sensitive, receptive, insightful that cannot be described, but providing an extremely rich creativity to every good and skilled perfumer. Jinkohol (2-epiprezizaan-7β-ol) Issue 1, September 2015, Tishrei 5776 The Israel Chemist and Engineer 29 Scientific Articles Softer than Jinkohol or Dihydrokaranone but imparting a special sweetness which combines extremely well with those described before and especially mixed with (-)-Guaia-1(10),11-dien15-al. The accord of these aroma molecules brings the smell of the mysterious woodiness of Agarwood oils, which bring the same results regardless of the different top note. O (8,12)-Epoxyeremophila9,11(13)-diene It is extremely woody but with very important amber gris notes as important as the woody ones. Karanone would mix extraordinarily well with pure amber chemicals such as Ambroxclassique (the original one containing ambrols) and by far the best, α-Ambrinol, Limbanol, Ambrostar, LaevoCetalox, Super Ambrox, Amber Xtreme, Ambrocenide, Cachalox, Ambrinoloxide, Dehydroambrox, Dihydro-γ-ionone, Timbersilk, Dextro Nor Limbanol, Trisamber, etc. O (+)-(4αR,5S)-Karanone. O O 2-(2-Phenylethyl)chromenone The best smoke comes from woods also rich on diepoxytetrahydro-2-2-phenyethyl-chromones.b These chromones stabilize and harmonize the smell provided by the volatile ingredients present in the wood and in the oils. O O O O DIepoxy-tetrahydro-2-(2-phenyethyl-chromones OH Very woody and smelling of Agarwood smoke Jinkohol II Jinkohol II character is somehow quite strange because when the oils are distilled, no more than 35 chromones present in the woods are detected. The presence of chromones is what makes the smell of the smoke richer, exalted, splendid, high, lofty and even glorious. The chromones do not come on the distilled products and only on the extracted ones by acetone, benzene, supercritical CO2, etc., being the most important ingredients for the smoke of Agarwood. Among them 2-(2-phenylethyl)chromones and 2-(2-phenylethyl)-tetrahydrochromenones are more mysterious that the other ones mentioned before. O O It seems the amount of chromones is what will make the fragrance successful, mostly by Royals, since a wood with 65% of chromones does not burn the same as a wood with only 10%. The chromones have nothing to do with the oils but the burning of these high noble ingredients with the chromones, produces spiritual peace and being in a “Platonic Pink Cloud” as described elsewhere by the author.2 O Having a lovely smell as other Agarwood ketones Eremophila-9,11-dien-8-one Eremophila-9,11-dien-8-one is a very unstable chemical and very dificult to detect through GC/MS since most of isomerizes to form more Dihydrokaranone during the conditions of the GC injector, being the noblest ingredients as happen in Vetiver too where the best smell is given by α-Vetivone, Dihydroβ-vetivone, Didehydro-β-vetivone, Didehydro-α-vetivone, Dihydro-α-vetivone, Khusimone, β-Vetivone, etc. Both oils are deined as noble “ketone” oils.3 2-(2-Phenylethyl)chromone 30 The Israel Chemist and Engineer Issue 1, September 2015, Tishrei 5776 Scientific Articles References H a. This molecule mixes very well with epoxieremohilladiene and has a beautiful note of β-Damascenone b. c. OHC (-)-Guaia-1(10),11-dien-15-al The beautiful note of (-)-Guaia-1(10),11-dien-15-al which is very rare on these chemical structures but also an orrisydiffusive and radiant smell with reminiscences of Irones and Dihydroirone. Its woodiness it is extremely soft, almost having soul and spirit. The studies made on the above sesquiterpenoids showed quite certainly that they are the most important when trying to rationalize this turning of the oils from their original and so diverse top note to the common precious woody note. A novel diastereoselective route to (4aS,5R)-4,4a,5,6,7,8hexahydro-4a,5-dimethyl-2(3H)-naphthalenone has been developed. The key step involves an asymmetric Michael addition of the corresponding chiral secondary enamines derived from (S)-(-)-1-phenylethylamine and (3R)-2,3dimethylcyclohexanone to 1-buten-3-one. This enone was successfully transformed into the eremophilane-type sesquiterpenoid (-)-Dihydro-karanone.c O (3R)-2,3-Dimethylcyclohexanone + 1. 2. 3. 4. 5. 6. 7. 8. N 9. (-)-((S)-?-Methylbenzyl)amine 10. (2,3-Dimethyl-cyclohexylidene)-(1-phenylethyl)-amine 11. 12. 13. O O (-)-Dihydrokaranone 1-Buten-3-one Sesquiterpenoides – The Holy Fragrance Ingredients – Part 1 M. Zviely and L. Ming, Perfumer & Flavorist (2013) 38(6), 52. The volatile and semi-volatile constituents of agarwood, the infected heartwood of Aquilaria species: a review. Naef, Regula; Flavour and Fragrance Journal (2011), 26(2), 73-89. A practical and eficient preparation of (-)-(4aS,5R)4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone: a key intermediate in the synthesis of (-)-dehydrofukinone; Schenato, R. A.; dos Santos, E. M.; Tenius, B. S. M.; Costa, P. R. R.; Caracelli, I.; Zukerman-Schpector, J. From Tetrahedron: Asymmetry (2001), 12(4), 579-584. Jeremiah, 6:20 Song of Songs, 4:14 Myrrh – Commiphora Chemistry, Lumír O. Hanuša, Tomáš Řezankab, Valery M. Dembitsky, Arieh Moussaieff; Biomed. Papers 149(1), 3–28 (2005) Kings I, 10:11 Müller PM, Lamparsky D. Perfumes: Art, Science & Technology. Amsterdam, New York: Elsevier; 1991. Bauer K, Garbe D, Surburg H. Common fragrance and lavor materials: preparation, properties and uses. 2nd ed. Weinheim: VCH; 1990. OBS: The volatile and semi-volatile constituents of agarwood, the infected heartwood of Aquilaria species: A review; Regula Naef, Flavour Fragr. J. 2011, 26, 73–89. (a) T. Nagashima, I. Kawasaki, T. Yoshida, T. Nakanishi, K. Yoneda, I. Miura.;IXth Int. Ess. Oil Congress, Singapore, 1983, p.12.; (b) M. Ishihara, T.Kitaura. JP 2004189643, 2004; (c) M. Ishihara, T. Kitaura. JP 2004231519, 2004 M. Ishihara, T. Tsuneya, K. Uneyama. Phytochem. 1993, 33, 1147 Eudesmane-Type Sesquiterpenoids in the Volatile Oilfrom Burseragraveolens; Chiyoki Yukawa, Hisakatsu Iwabuchi, Sadao Komemushi and Akiyoshi Sawabe; J. Oleo Sci., Vol. 53, No. 7, 343-348 (2004) M. Zviely and C. Hong; Perfumer&Flavorist (2009), 34(1), 26. M. Zviely; Perfumer &Flavorist (2009), 34(12), 20. M. Zviely; Perfumer &Flavorist (2012), 37(2), 46. O HO O O 3-(1-Hydroxy-1-methyl-ethyl)-4a,5-dimethyl4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one 2,3-Dimethyl-2-(3-oxo-butyl)-cyclohexanone O Acetone O (4aS,5R)-4,4a,5,6,7,8-Hexahydro-4a,5-dimethyl 2(3H)-naphthalenone Issue 1, September 2015, Tishrei 5776 The Israel Chemist and Engineer 31