World's MOST Celebrated Perfume Molecules: March 2013

Alpha and beta damascone

Greetings! Apparently, many of us like to aromatize ourselves especially ladies! Perfume (as according to thefreedictionary.com) is a substance that emits and diffuses a fragrant odor, especially a volatile liquid distilled from flowers or prepared synthetically and also a pleasing, agreeable scent or odor.

Perfume = Fragrance

So what actually perfumes you and I?

They are alpha and beta damascone, hedione, alpha and beta santatol which are some of the most important fragrance ingredients.

They are all organic molecules and we love organic chemistry. Well, let’s look into the first one, alpha and beta damascone.

With the suffix that ends with –one, it must be from a ketone family. Alpha and beta damascone are rose ketones derived from the Bulgarian rose oil.

Molecules	Alpha damascone	Beta damascone
Structural formula
IUPAC name	1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-but-2-ene-1-one	(E)-1-(2,6,6-trimethyl-1-cyclohexenyl)but-2-en-1-one
Empirical formula	C13H20O	C13H20O
Scent	a strong rose odor with a pronounced fruity green apples scent	A complex odour of rose, plum, blackcurrent, wine and tobacco
Solubility	Soluble in alcohol	Soluble in alcohol

What are the Uses of these damascones?

They are used in alcoholic solution, antiperspirant cream. Deodorant spray, shampoo, and soap. α-Damascone (rose -apple note) is highly effective in enriching odor of natural as well as artificial aromas. It is used to add a sweet floral woody odor with green berry undertones. Beta damascone emits a fruity floral blackcurrant plum rose honey tobacco. Beta-damascenone and Beta-damascone (blackcurrent- plum note) remain two of the most important fragrance ingredients.

Ever wondered how are these damascone being synthesized?

One of the examples are preparing 1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-but-2-ene-1-one ( alpha damascone) from 2,6,6 – trimethyl-1-cyclohexene.

2,6,6 – trimethyl-1-cyclohexene is added to the stirred suspension that consists of:

cyclohexane

+ ZnCI +

Crotonic anhydride

Cyclohexane- (100ml) + ZnCI (20gms) + (crotonic anhydride 150gms) for 45 minutes at 80 C. The mixture is cooled to room temperature and (aq, 500 ml of 5%) is poured into the mixture. The cyclohexane layer containing the product (II) is separated and washed with water to make it neutral. The organic layer is dried over with Na2SO4 followed by filtration and distillation under atmospheric pressure which is further fractionally distilled to obtain alpha damascone (70 gms) and a purity of 95%.

alpha damascone

Who was one of the 1st fragrances to incorporate damascones into its rose veiled structure?

Nahema by Guerlain (1979) was one of the first fragrances to incorporate damascones into its rose veiled structure. Damascones decorate the rose notes in the way that gold jewelry enhances the beauty of princesses from the Arabian Nights tales by which Nahema was inspired. Indeed, one of the biggest successes of the 1980s was another damascone overdosed creation, Christian Dior Poison (1985). While alpha-damascone is fruity and floral, with a distinct camphorous element, beta-damascone can be described as gourmand, with floral and tobacco-like aspects. Its honeyed plum facet complements the spicy heart of Poison, while offering a beautiful sweet prelude to the ambery base.

References:

http://www.surechem.org/index.php?Action=document&docId=407632&db=USPTOA&tab=desc&lang=&db_query=2%3A0%3A&markupType=all

http://www.prasadorganics.com/AlphaDamascone.html

http://boisdejasmin.com/2006/02/fragrance_ingre.html

http://www.thegoodscentscompany.com/data/rw1000881.htmlhttp://www.chemicalbook.com/ChemicalProductProperty_EN_CB6755373.htm

Sandalwood tree

Sandalwood- Alpha and Beta Santalol

Category : Herbs & Supplements

Generic Name : Sandalwood

Botanical name : Santalum album
Family : Santalaceae, the sandalwood family

Synonyms : Alpha-santalol, beta-santalol, East Indian sandalwood, Sandalwood oil, white sandalwood.

Sandalwood

Santalum album is a medium-sized evergreen tree with opposite, leathery leaves. The small tree is native to East Asia but has been known in the sub-continent for millennia. The exact origin of sandalwood is not known. It is found in tropical Asia through Australia to Hawaii. Like most species of the genus Santalum it is a root parasite, tapping the roots of other species for water and inorganic nutrients. The wood of Santalum album is highly aromatic. The light sapwood is used for wood carvings, whereas the darker wood from the core is steam distilled, yielding the precious sandalwood oil. Bits and pieces are used for incense sticks, etc. One of the most famous sites of cultivation is Mysore in India. The trees must be 30 years before the oil production pays off. The yield is not more than 5 %.

Freshly distilled sandalwood oil has a wonderful odour - an extremely soft, sweet-woody and delicately animal-balsamic odour. For thousands of years it has been one of perfumery's most precious items. It forms the basis of heavy oriental compositions, and creates delightful combinations with rose, violet, tuberose, clove, bergamot, lavender and a lot of other fragrant materials. Sandalwood oil mainly consists of a number of closely related sesquiterpene (a class of terpenes that consist of three isoprene units and have the molecular formula C15H24). Alpha and beta Santalol are constituents of the prized East Indian sandalwood oil. They amount to more than 90 % of the oil, beta-santalol being the most important character impact compound. Müller and Lamparsky (perfumes expert) describe the odour of the two isomers as:

Alpha- santalol

Beta- Santalol

Alpha-santalol --- A relatively weak, slightly woody odour reminiscent of alpha cedrene.
Beta- santolol --- Typically sandalwood odour, with powerful woody, milky and urinous tonality
*To have a 3-D look on the structure of Alpha and Beta Santalol, please visit
http://www.leffingwell.com/chirality/santalol.htm

Uses

Sandalwood oil is used in perfumes, skin and hair preparations. As a cosmetic it has moisturising, astringent, balancing, stimulating properties soothing and anti-bacterial properties on the skin. It can be blended with other plant-derived extracts in hair oils and body lotions and is recommended for dry and aging skin. The oil is also used in perfumery, both in India and Europe. It has a characteristic of sweet, woody odour which is widely used in the fragrance industry. It has excellent blending properties and the presence of a large proportion of high-boiling constituents in the oil also makes it valuable as a fixative for other fragrances. The highly aromatic wood of the sandalwood tree is widely used in South Asia for religious and medicinal purposes and it is a prime source of incense and perfumes.

New artificial Sandalwood odorants

Beta-Santalol was synthesized in the laboratory for the first time in 1990 by an 11-step synthesis. Today, the finest substitutes are derived from campholenic aldehyde, for instance Santaliff ®, produced by IFF (International Flavours & Fragrances Inc.). Javanol ®, by Givaudan, is a new 'cyclomethylene analogue' of this compound. It turns out that substituting the alkene double bonds with the almost isosteric cyclopropane rings creates increased olfactory power and stability. Javanol ® has a strongly diffusive, natural, creamy sandalwood note with rosy shadings. Interestingly, 3,7-dimethyl-7-methoxy-2-octanol also has a fine (but weaker) sandalwood character. It was formerly produced by Bush Boake Allen under the name of Osyrol ® (Osyris is another genus of the sandalwood family).

Problems Faced

Sandalwood trees are the source of an attractive and fragrant wood. The wood is popular for wood carving, and is the source of sandal oil. The oil is valued for perfumery and incense. Sadly, the popularity of sandalwood has led to severe conservation problems. India accounts for 90% of world production of sandal oil, but production is declining as too many trees are cut down. East Indian sandalwood and other species have also been harvested for their oil in Indonesia, Fiji and Australia. Overharvesting has been a common problem and USA and France are two of the biggest importers.

References

http://www.rsc.org/chemistryworld/Issues/2009/February/TheSweetScentOfSuccess.asp

http://www.bojensen.net/EssentialOilsEng/EssentialOils27/EssentialOils27.htm

http://www.healthline.com/natstandardcontent/sandalwood

http://www.kew.org/plant-cultures/plants/sandalwood_landing.html

Hedione

Marian Bendeth, the president of Sixth Scents and also the Global Fragrance Expert and consultant to many top perfume houses has quoted that “Perfume is like cocktails without the hangover, like chocolate without the calories, like an affair without tears, like a vacation from which you never have to come back.” Perfume is an asset which lifts a person charm. When we talk about perfumes, we’ll think of the known fragrance compound in perfume chart topper, Hedione.

Figure shows the structure of Hedione.

Hedione is derived from the Greek word “hedone,” defining as pleasure which is a fitting moniker for this luminous and compelling note. Hedione, also known as methyl dihydrojasmonate (Methyl 2-(3-oxo-2-pentylcyclopentyl) acetate) is an ester, an aroma chemical which smells vaguely identical to jasmine. It belongs to a very complicated and rich family of molecules present in the jasmine like flowers. This jasmonate family might be described as the quintessence of jasmine. (Octavian Coifan, n.d.) It is often used not only as substitution for jasmine absolute, but also due to its own fresh-citrusy and green tonality.

The synthesis of Hedione is through a sequence of condensation reaction. The synthesis begins by a key intermediate 2-pentylidene cyclopentanone, forming a condensation starting from cyclopentanone and n-valeraldehyde, followed by isomerisation, Michael addition and a selective decarboxylation. The products of synthesis are four stereoisomers, in which only one of them truly contributes to the jasmine odour, which is the (+)-cis methyl dihydrojasmonate, while the others are thought to modulate other fragrances. In 1989, Nippon-Zeon had successfully converted the trans-form into cis-form through isomerisation process. In the mid-1990s, the first asymmetric synthesis of the desired (1R)-cis-Hedione using a Ru-(-)-(R, R)-Et-DuPHOS catalysed asymmetric hydrogenation; and the other asymmetric routes have since be developed. It is used in various fine fragrances for more than 40 years and is Fermenich’s top seller in terms of volume.

Hedione simply gives an elegant and warm floral jasmine note with a citrus freshness, which possesses high diffusion, long-lastingness and tenacity. It is much favorable and is highly used as it develops a beautiful natural smoothness and radiance in a wide range of perfume types. It’s authentically pure and aromatic presence is one that cannot be easily replaced by any other fragrances molecules, nor compounds.

Hedione has been placed under the lime light in perfume history when it was first discovered by Firmenich researcher, Edouard Demole in the early 1960s where he was analyzing the composition of jasmine essence. Its highlight was when its usage of 2% was seen in Christian Dior Eau Sauvage, created by Edmond Roudnitska in 1966. A layer of luminous jasmine against the backdrop of herbs, patchouli, woods and coumarin makes Eau Sauvage revolutionary in its ability to interpret floral notes in the domain of masculine perfumery. (Victoria, October 26, 2005.) Its influence in perfumery field then rose with the latter presence of fragrances like Eau de Rochas and Ô de Lancôme, Christian Dior Diorella (1972) and Comme de Garçons Odeur 53, all created with the inspiration of Hedione’s refined aura.

In conclusion, Hedione is just simply unique and precious in the sense of its characteristic: the long lasting light jasmine note that remains in the air after it evaporates, always giving a refreshing and floristic feel. It is a much appreciable fragrance compound for synthesizing and creating better products, yet always owning the niche demand in market.

Reference:

1) Victoria, October 26, 2005. [Online]. Hedione Luminous Jasmine : Fragrance Ingredient.

<http://boisdejasmin.com/2005/10/fragrance_ingre-2.html>.

2) Jeb Gleason-Allured, 23 August 2011. [Online]. Let There Be Light: 50 Years of Hedione.

Available from: <http://www.perfumerflavorist.com/fragrance/application/finefrag/128264148.html>.

3) Octavian Coifan, n.d. [Online]. Hedione 50 years - anniversary perfume & scent chemistry.

Available from: <http://1000fragrances.blogspot.com/2012/06/hedione-50-years-anniversary-perfume.html>.

Sunday 17 March 2013

Alpha and beta damascone