Perfume Ingredient: Salicylates ~Smell, Role and Function

Savouring Vanille Galante by Hermès now that the weather is getting cooler again, I am struck by its "solar" effect, a warming, "open", bright effect that is rendered through the use of salicylates: benzyl salicylate, cis 3 hexenyl salicylate, and iso amyl salicylate. To the perfume student these molecules present fascinating facets on the path of creation because salicylates encompass complimentary aspects and aid diffusion, making fragrances open up and "expand" in a sunny, exhilarating way. Gardenia, tiaré, and frangipani accords are usually built on salicylates and their summery vibe warms our heart even in winter. In this article we're going to occupy ourselves with the ones which are most often used in fine fragrances.

Benzyl Salicylate (benzyl ortho hydroxy benzoate) is an almost colourless liquid that has a mild balsamic, sweetly floral note possessing excellent blending capabilities. Often used ~like foundation is for make-up~ as a base for heavy florals such as ylang, gardenia, jasmine, lily etc. It is also used in functional products such as soap, shampoo and fabric softener. Along with Methyl Salicylate, salicylates “turn the most banal floral composition into a real perfume, with majestic weight and sweep” divulges Luca Turin. However some people are anosmic to it, including some perfumers. Guy Robert could not smell benzyl salicylate at all, but could instantly recognize its presence in perfume: “I recognize it as if it were a friend seen from behind in a crowd, by the cut of his shoulders”. Indeed in the words of nose Bernand Chant “it produces a diffusing, blooming effect very pleasing to the public”. Many orchid fragrances are built on salicylates, while the mysterious emerald glow of the vintage Je Reviens is also due to them. Coupled with eugenol and isoeugenol, the effect becomes almost carnation-like with its clove tint. The magic of benzyl salicylate can be best experienced in the archetypal floral bouquet of L’air du Temps featuring an overdose of the ingredient. Its progeny included Wind Song, Norell, Estée, Charlie, even Angel! However the recent restrictions on the use of benzyl salicylates have taken their toll on many floral fragrances, L’air du Temps included, which simply do not smell as they used to.

Methyl salicylate (salicylic acid methyl ester or oil of wintergreen ~because it is present in lots of evergreens such as birch and also rhododendrons~ and commonly featured in arthritis and muscle body rubs but also in Life Savers) has a green glow with camporeous aspects. Naturally occuring in tuberose, jasmine and hyacinth absolutes, as well as ylang ylang and neroli oil, it provides that characteristic eucalyptus-mint nuance of Tubéreuse Criminelle and to a lesser degree Carnal Flower. It is also a big ingredient in birch tar, used in Russia in treating leather and therefore associated with Cuir-de-Russie-themed fragrances, modernly interpreted in Dzing! and Bulgari Black. Also present in cassie absolute, so it seems to be the bridge between those and Une Fleur de Cassie; the connection being that acacia bark (the inspiration behind the latter) was also used in treating leather, in France.

Amyl salicylate (pentyl ortho hydroxy benzoate) is a colourless liquid related to coumarin olfactorily, frequently used to round off a composition and fix fine fragrance (floral or non-floral) even though not a constituent of volatile oils. The molecule is also referenced as orchidee, trefle or trefol due to its orchid-like lightly sweet floral and herbaceous-green aroma and its inclusion in L.T. Piver's 1898 mythical Le Trèfle Incarnat. A tiaré accord built on amyl salicilate is used in the Dior Bronze range to impart the lightly powdery floral nuance which serves as a reminder of beloved products of sunbathing (see below). Chances are you've smelled amyl salicylate in your favourite shampoo, deo, hair spray or fabric softener too as it is so prevalent in those products or used it in your anti-rheumatism prescription.

Ylang ylang (cananga odorata), a very frequent floral essence in perfumery and a constituent in Vanille Galante which prompted these syllogisms in the first place, naturally encompasses salicylates and eugenol (a spicy ingredient); the former in the form of benzyl salicylate is the basic ingredient in the Ambre Solaire suntan lotion, with its white flowers tinge, which is synonymous with summer vacations to many Europeans (The ingredient first entered the composition for its sunscreening properties and later overstayed thanks to the fond reactions of users to its smell). Even the humble aspirin is a product of salicylates. The magic of salicylates is that they creep up on you from the most unlikely places!

Ref: E. Gildemeister, The Volatile Oils

Pic via edwan.blogspot.com, Ambre Solaire ad via mtblog.self.com

Myth Debunking: Scented Candles Accused of Causing Cancer? The Truth Revealed

If you're any phobic about the big C disease at all, you'd bettter skip this article or you'll get ideas. Or rather you should read it to decipher another bunch of C, the kind that has you nodding your head incredulously and exclaiming "my, my!"

After all the IFRA brouhaha that erupted last spring concerning the strictening of perfumery raw materials control and percentage allowed in commercial products {you can read about it clicking the highlighted links}, there comes intimidating news concerning even the humble ~or not so humble, depending on your decadence quota and disposable income~ scented candle! According to a fun two-sided approach on the Telegraph.co.uk, in which scented candles are praised and trashed respectively by Becky Pugh and Nick Collins based mainly on aesthetic and cultural reasons, it also transpires that "Researchers at South Carolina State University have discovered that the humble scented candle releases potentially harmful amounts of toxins". How scary, right?

To be thorough we investigated this info a little (our geeky nature cannot be hidden for long). Here are some of the claims of the research:

"This study characterized the products of emission by individually burning 91 candles inside a stainless steel combustion chamber and determining specific emission rates of soot, benzene and lead. Candle soot was typically less than 1 µm, contained up to 66% elemental carbon and carried numerous adsorbed organic compounds including dibutyl phthalate, diethyl phthalate, toluene and styrene. Volatile organic compound emissions included benzene, styrene, toluene, ethyl benzene, naphthalene, acetylaldehyde, benzaldehyde, benzene, ethanol, and 2-butanone (methyl ethyl ketone). Analysis for lead revealed some candles emitted significant quantities of aerosolized lead during combustion".

The quote originates from "Characterisation of Scented candle emissions and associated public health risks" by J. David Krause, Department of Environmental and Occupational Health, College of Public Health, University of South Florida, August 1999.

Please note the date folks: 1999!!! I mean, geez, a whole decade ago! Wouldn't there be more info available till now and wouldn't companies have cottoned up to those claims so as to reduce the hearmful ingredients as much as possible? After all nail polish comes sans toluene or phtalates anymore, therefore why would candles be far behind? And just how many of you burn candles inside a stainless steel combustion chamber, unless you're fetishizing KZ-Dachau (in which case what are you doing reading this venue?). Somehow this piece of "news" is making the rounds on the Internet (see this article on The Daily Mail for some quotes by doctors or this one spinning off the info) and one is picking it after the other which usually has my antennae up on something fishy being behind all that. It's either that "there are no news in August" or...something else. There is the snippet mentioned that "The neighborhood around NPR HQ in Washington is crawling with chemists attending a big meeting of the American Chemical Society this week". Could it be comparable to the war declared on fragrances and the egoes involved in the academic world?

It's quite logical and sane that Nick Collins exclaims on the Telegraph:

"One really has to respect the brass neck of the designers who make these things, because they have got the women of this world eating out of the palm of their hand [...]If candles weren’t primarily an evening product, one might call it daylight robbery – the market in candles is believed to be worth a jaw-dropping £125 million, 90 per cent of which are bought by women. What’s more, the market has increased threefold in the past three years".

Who can argue with that? It's a way to make the economy roll! Still I would like to focus more on this attitude as presented by Becky Pugh:

"Being, without doubt, a luxury item, it's hard to justify the cost, especially as the inconvenient truth is that the cheaper the candle, the sicklier its fragrance. So although every homeware store, and even supermarket, now stocks a range of them, you need a fairly posh one for it to be worthwhile".

Indeed one would presume that the real danger healthwise, the lead-treated wicks, are often eliminated from more expensive candles, while paraffin (a cheap by-product of petroleum) is less opted for in favour of soy wax. "Candles made from soybean-derived wax didn't show the same pattern of potentially toxic emissions" [quote source] although scientists are wary of cautioning this is merely qualitative info. Did the soybeans manufacturers lobby up for their product or was the Candlemaking Foundation caught asleep at the wheel? From the following ~published on the above source~ it transpires that something is rotten in the kingdom of Denmark: Scott Hensley notes:

"One more caveat: the work is funded by the Department of Agriculture, which wouldn't mind if soybean-based candles became the rage. As a summary of the research under the headline "Soybean Candles For Healthy Life And Well Being" puts it: 'By replacing paraffin wax with soy wax in candles, an estimated 60 million pounds of soybeans would be required for annual candle production. This requirement will have a direct economic impact on soybean farmers as well as a health and environmental impact in this country'."

Draw your own conclusions!

Of course one could also claim that soy is one of the most heavily genetically-modified products on the planet (and it's in the top 3 actually) so that would open a whole new can of worms, but you know what I am getting at, don't you! And to further this, there is also the fact of a scientist for one company going public on MSNBC that an industry study a few years ago could essentially not differenciate between paraffin-based and vegetable-based candles' emissions!!

Personally I would be wary of linking cancer to any of these products: cancer is increasingly identified as being a genetical predisposition (and believe me I know, I have family members working in cancer research at top notch institutions), meaning you will get it anyway if you're so DNA-inclined and panic certainly doesn't help, nor would banning scented candles bring any significant results; I'd venture that industrial and urban air pollution is hundreds of times more detrimental in exarcebating cancer growth. Like an intelligent commenter noted: "I think the only way to avoid cancer-causing materials these days is to move into a bubble. Unless the plastic turns out to be a cancer-causer too…which it will". Another writer at The Guardian "gets" it, although to her scented candles are a no-no due to other reasons; but that's totally cool and she might have a point (the article is worth a read).
The claim that scented candles "could trigger asthma attacks or skin complaints (ie/eczema)", according to the American Chemical Society's annual conference, that I can believe. But surely the solution to that would be quite simple: avoid whenever possible. Like with smoking, a certain regard for other people's comfort goes a long way...

David's The Death of Marat has been cleverly manipulated to include Cire Trudon candles in papermag.com. I found it supremely fitting! Aqua di Parma candles via splendora.com

The Galaxy Tastes of Raspberries and Smells of Rum

Apparently the unifying logic of the Universe has a sweet n' sour tooth! Ethyl formate, which gives raspberries their flavour and smells of rum, has now been found in deep space, the center of our galaxy. Scientists from the Max Planck Institute for Radio Astronomy in Bonn, were searching for evidence of amino acids ~and consequently evidence of the building blocks of life~ in a giant dust cloud at the heart of our Milky Way when they came up with the surprising discovery.

Amino acids found in interstellar space can be said to be astrobiologists' Holy Grail because amino acids are the building blocks of proteins (critical for complex life to exist anywhere in the universe); a fact which would therefore indicate the possibility of emerging life on other planets after being seeded with the molecules.
In 2008, astronomers Arnaud Belloche and Robin Garrod almost managed to come across amino acids in space when they discovered amino acetonitrile, a molecule that can be the building block of aminoacids and consequently proteins. Previously, astronomers had detected a variety of large molecules, including alcohols, acids and chemicals called aldehydes. Those chemicals form when pre-existing chemicals on dust grains, such as ethanol, link together to make more complex chains. But recent discoveries suggest the molecules are as large as the simplest amino acid, glycine, which is heartnening.

The astronomers used the IRAM telescope in Spain to shift through signals and electromagnetic radiation emitted by Sagittarius B2, a dust cloud around a newborn star at the centre of our galaxy. Failing to locate any aminoacids, they nevertheless came across ethyl formate, a chemical responsible for the flavour of raspberries. But ethyl formate has another distinguishing quality that ties it with scent ~it smells of rum! Talk about boozy -inspired creation! Yet evidence for the deadly chemical propyl cyanide was also present in the same cloud, making them the largest yet discovered molecules in deep space and food for philosophical thought around the duality of life and death; but perhaps that's fodder for another discussion.

In a witty quip Belloche replied as to whether the galaxy tastes of raspberries that: "[Ethyl formate] does happen to give raspberries their flavour, but there are many other molecules that are needed to make space raspberries!" Dr Belloche and his colleague Robin Garrod at Cornell University in New York have amassed nearly 4,000 distinct signals from Sagitarius B2, analysing about half of them so far. "We have identified around 50 molecules in our survey, and two of those had not been seen before" said Belloche. The results are being presented at the European Week of Astronomy and Space Science at the University of Hertfordshire.


News via Guardian.co.uk, pic Raspberries, Rubus ideaus L, after passive self-pollination (left and middle) and open insect pollination (right). (Photo by Jim Cane, Bee Research Institute, Longan, USA) via what-is-this.com

Rotten eggs: Not what you Expected on the Last Word on Sexy!

If you have ever played with those filth-ampules at school that had the smell of vomit, excrement or rotten eggs, in the hopes of cutting classes due to the stink, little did you imagine that one of these days you'd find yourself looking at them with new appreciative eyes! The rotten eggs one especially, which you swore was the most abominable smell in the whole planet and which infested school halls for weeks almost. Well prepare to be given the shock of a lifetime and I am not making this up!

According to a study published in the scientific journal of the Proceedings of the National Academy of Sciences led by Professor Giuseppe Cirino of the University of Naples in Italy, studying eight men who had sex-change ops, the claims are: "We found that hydrogen sulphide is involved in human penile erection". As you might have uncredulously surmised by now hydrogen sulphide is a major odour constituent in nothing more aromatic than rotten eggs!

"The bizarre finding could help doctors to develop a more effective version of the sex drug Viagra. [...] A gas called hydrogen sulphide – also released when eggs rot and from the exhausts of cars with catalytic converters – is given out by men just before they have sex. Tiny amounts of it are released by nerve cells in a man's private part to prepare it for intercourse, a study found. The gas causes muscle cells in the region to relax, boosting blood flow, and leading to a better erection. Viagra, however, harnesses a different chemical – nitric oxide – to give users a boost. But one third of men have found the drug ineffective."

Hydogen sulphide has the chemical type H2S, is a colourless and flammable gas, and is produced in mammalian organisms from cysteine by the effect of various enzymes. It can also be found in volcanic gases, swamps and sewers via anaerobic digestion (that means in the abscence of oxygen) and is partially responsible for the foul odor of flatulence as well! Another proof that not everything we think applies in matters of science! Although very pungent at first, it quickly deadens the sense of smell, so potential victims may be unaware of its presence until it is too late...Let's not forget the Permian-Triassic extinction about 252 million years ago!(I'm so itching to crack a joke right now).

I guess the order of the day is: Ladies, you're stongly advised not to rely on this as a man-ensnaring device; and gents, please don't try it as a boost to your manhood!

I found the very interesting article through Minette of Scent Signals. You can read the whole article here.
Pic of partial Wilkinson Quattro Titanium ad via invertospot.com.

Myth Debunking 1: What Are Aldehydes, How do Aldehydes Smell and Chanel No.5

Ask any aspiring perfumista about aldehydes and you will hear that they are synthetic materials first used in Chanel No.5, that thanks to them this is the first and the prototype of synthetic fragrances and that aldehydes themselves have a champagne-like, sparkly, fizzy odor that makes the fragrance fly off the skin. This is what they have been told time and again. Ask any seasoned perfumephile and you will hear that aldehydes have a waxy, citrusy or rosy aroma, like snuffed-out candles (Luca Turin was instrumental to that with his references appearing in “Emperor of Scent”). The truth? It’s a little more complicated than either!

It’s a fact that aldehydes became famous through their introduction in copious amounts into the formula of Chanel No.5 in 1921. However No.5 is definitely NOT the first fragrance to feature synthetic aldehydes :

~"Though Chanel No. 5 is recognized as the first Aldehydic fragrance, created in the mid-twenties, the truth is that the first Aldehydic fragrance was Rêve D'Or(Golden Dream), [1]created in 1905 by Armingeat." (sic[2]).

Nor is No.5 the first modern perfume to feature synthetic components (that honor belongs to Fougère Royale -Royal Fern- by Paul Parquet for Houbigant in 1882). Aldehydes themselves are organic compounds present in various natural materials (for instance natural citrus essences such as the one from orange rind, rose oil, pine essence, citronella and cinnamon bark ~they even appear in bovine heart muscle!). Several essence reconstitutions by chemists involved using aldehydes as various types can also be synthesized in the laboratory.

Aldehydes (same as ketones) are organic compounds which incorporate a carbonyl functional group (that's C=O). The carbon atom of this group has two remaining bonds that may be occupied by hydrogen or alkyl or aryl substituents. If at least one of these substituents is hydrogen, the compound is an aldehyde. If neither is hydrogen, the compound is a ketone. The majority of aldehydes and ketones have strong odors. Ketones generally have a pleasant smell and they are frequently found in perfumes (e.g. muscone in musk-smelling colognes). They are also used in food flavorings. Aldehydes vary in smell with most of the lower molecular weight smelling bad (rotten fruits), yet some of the higher molecular weight aldehydes and aromatic aldehydes smell quite pleasant and are thus used in perfumery. Formaldehyde is the simplest aldehyde with a central carbon atom bound to two hydrogen atoms (H2C=O). Discovered in Russia by A. M. Butlerov in 1859 it is very reactive, used in dyes, medical drugs, insecticides and famously as a preservative and embalming fluid.
Aliphatic aldehydes possess intriguing smells outside the realm of simplistically nice: butyraldehyde for example smells of rancid butter (from βούτυρο/butyro which means "butter" in Greek)! Acetaldehyde is the name of the shortest carbon chain aldehyde and is one of the oldest known aldehydes (first made in 1774 by Carl Wilhelm Scheele). Its structure however was not completely understood until Justus von Liebig determined the constitution of acetaldehyde 60 years later, described its preparation from ethanol, and baptised this chemical group “aldehydes”.

Hardly a fragrance exists without some kind of aldehyde in it, which incidentally makes insisting the greatness of No.5 is due to its synthetic materials comparable to saying that the Pyramids are monumental because of their shape alone. It is the cleverness of marketing and the propagation of a myth that No.5 was meant to evoke an unnatural smell (because supposedly Coco Chanel insisted that she wanted a perfume smelling of a woman and not of flowers ~"women do not want to smell of a bed of roses") which gave rise to this confusion. Chanel No.5 and No.22 later owe their vivid sprakle to a specific subgroup of aldehydes which are called “fatty”: strings of carbon atoms (between 8 and 13) coded in accordance to that number of atoms (ie.C8) with nomenclature deriving from Greek numerics, such as octanal from οκτώ/octo (=eight), in which each of the 8 carbon atoms is connected to two hydrogen atoms. The “bouquet” of aldehydes C10, C11, and C12 in Chanel No.5 became so popular that all consequent “aldehydic fragrances” used that sequence of aldehydes, giving a fizzy perfume-y scent that is quite characteristic with the direct result of having the perfume lover confused as to how aldehydes themselves smell. Fatty aldehydes have a citrusy or floral note, and a pronounced fatty/waxy/soapy tone which is very apparent if you consider a modern fragrance that uses them in high ratio: Sicily by Dolce & Gabbana. The soapy feel is unmistakeable! As an exercise compare that smell with your Chanel No.5: you will pick up the soapy facets in that one as well. Another reason that they read as “soap” is exactly because they have been used in the production of soap for years to give that fresh lemony feel.

Most widely used aldehydes in perfumery are C7 (heptanal, naturally occuring in clary sage and possessing a herbal green odour), C8 (octanal, orange-like), C9 (nonanal, smelling of roses), C10 (decanal, powerfully evocative of orange rind; Citral, a more complicated 10-carbon aldehyde, has the odor of lemons), C11 (undecanal , “clean” aldehydic, naturally present in coriander leaf oil~also used is unsaturated C11 undecen-1-al), C12 (Lauryl aldehyde evocative of lilacs or violets), C13 (waxy, with grapefruit tone)and the infamous C14 peach-skin note of Mitsouko: technically not an aldehyde, but a lactone ~gamma undecalactone.

Often the compounds are patented under commercial names; therefore their true nature remains arcane even to perfume lovers who might have seen them mentioned. For instance Triplal, a patented molecule by IFF: its chemical name is 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde. Its smell? Powerfully green and herbal, like crushing ligustra leaves between fingers. None of the characteristic aldehydes of Chanel No.5!
One interesting ingredient is phenylacetaldehyde which has a pronounced green note (top in natural narcissus and thus used to recreate a narcissus note in perfumery). The hydrocinnamic aldehydes are another family of materials from the manipulation of benzene and their odor profile resembles lily of the valley (muguet) and cyclamen. One of them is the famous Lilial (patented name for lily aldehyde; also known as Lilistralis), widely used in the replication of that elusive natural essence, lily of the valley. Another is Cyclamen aldehyde (usually produced with cumene as a starting material).
Aromatic aldehydes have very complex chemical structures but are the easiest to identify by smell. Anisaldehyde smells like licorice. Benzaldehyde on the other hand, has an odour profile of almonds and has several chemical constituents: cinnamaldehyde, amylcinnamic aldehyde, hexylcinnamic aldehyde. Condensation of benzaldehyde with other aldehydes gives a series of α-substituted cinnamlaldehydes, the lowest member of which is used in the production of cinnamyl alcohol, very important in the production of spicy perfumes (cinnamon note). Higher members, on the other hand, such as amylcinnamic aldehydes (ACA) and hexylcinnamic aldehyde (HCA) project a fatty jasmine impression despite their abscence from natural jasmine oils! Most synthetic jasmine perfumes today use one or both because they are inexpensive (Their fibre-substantive qualities also make them perfect candidates for laundry detergents and fabric conditionners). The hawthorn or aubépine note, rendered synthetically in perfumes for several decades, is produced via anisic aldehyde (p-methoxy benzaldehyde) and it has been sublimely woven into the gauzy cloth of Après L’Ondée by Guerlain (where it sings along with heliotropin). Additionally, the aldehyde vanillin is a constituent in many vanilla-scented perfumes. So nothing is as simplistic as one might assume!

Aldehydic fragrances include (click links to read corresponding articles/reviews): Chanel No.5 and No.22, Lanvin Arpège, Guerlain Liu and Véga, Worth Je Reviens, Millot Crèpe de Chine , Balecianga Le Dix, Revillon Detchema, Caron Fleurs de Rocaille (not Fleur, singular), Infini and Nocturnes, Myrurgia Joya, Jean-Charles Brosseau Ombre Rose , Molyneux Vivre, Lancome Climat, Givenchy L’Interdit, Piguet Baghari, Madame Rochas and Mystère by Rochas, Rive Gauche by Yves Saint Laurent , Paco Rabanne Calandre, Estée Lauder Estée, White Linen, Pure White Linen, Van Cleef & Arpels First, Nina by Nina Ricci (the old formula in the ribbed bottle), E.Coudray Musc et Freesia, Bill Blass Nude and Amazing, Hermès Amazone, D& Sicily, Divine L’Ame Soeur, Serge Lutens La Myrrhe, Frederic Malle Iris Poudre, Ferré by Ferré, Agent Provocateur Maitresse, Annick Goutal Folavril, Le Labo Aldehyde 44.
Hermès Calèche is poised between floral aldehydic and floral chypre in some taxonomies.

[1]Bernand Chant, British Society of Perfumers 1982
[2]Armigeat is perfumer Pierre Armigeant (1874-1955) who composed Floramye and Azurea for L.T.Piver

Painting Gueridon 1913 by Georges Braques, courtesy of allposters.com. Chanel makeup ad via Bellasugar.