Perfumery Material: Coumarin, Tonka Bean & the Fougere accord

Open any perfume guide with fragrance "notes" or any online discussion or blog post on perfume description and you're bound to stumble on coumarin; one of the most common materials in many fine fragrances but also several body products, cosmetics and functional products. Its rich history goes back to the beginnings of modern perfumery in the late 19th century, bringing us right at the moment of the nascent concept of perfumery as a mix of organic chemistry and nature's exploitation. Coumarin as such is a synthesized material in most perfumes, but it's also found in abundance in natural products, such as tonka beans (Dipteryx odorata) where it is the principle aromatic constituent (1-3%). In fact the name derives from "cumaru", an Amazonian dialect name for the Tonka bean tree.

• Origin & function of coumarin

Chemically, coumarin is a benzopyrone (1-benzopyran-2-one) which, apart from tonka beans, also occurs naturally in vanilla grass (Anthoxanthum odoratum), sweet woodruff (Galium odoratum), sweet clover (Meliotus L.), sweet grass (Hierochloe odorata) and cassia cinnamon (Cinnamomum aromaticum) among other species. In short, it's rather sweet, as you might have surmissed by now, and evokes cut grasses. You'd be correct to assume both facts, but that's not all: Although coumarin in perfumery does add a certain sweet note of mown hay or freshly cut grass with vanilla overtones, it's really bitterish in flavour in high concentrations (its -now banned- inclusion in food would attest that). Therefore theorizing its plant origin one would assume it's produced by plants in order to defend themselves from predation. After all it's also present in cherries, strawberries, and apricots, prime targets for birds. You might have even seen it featured in your rodent pesticide: don't be alarmed (coumarin is included in miniscule quantities in foodstuff anyway), but now you know why!

• History of coumarin discovery & synthesis

Natural perfumers used and continue to use tonka bean absolute and tonka in powder form, as well as deer's tongue, a herb with brittle leaves to render a coumarin note. But the story of coumarin is largely one of organic chemistry. The component was isolated by A.Vogel in 1820, but the laboratory synthesis of coumarin first happened in 1868 from coal tar by W.H.Perkin (who gave his name to "the Perkin reaction" used to produce it). It took another year to produce it in an industrial scale at Haarmann & Reimer. The consequent memorable inclusion of synthesized coumarin in Jicky (Guerlain 1889) and earlier in Fougère Royale (Houbigant 1882) was the kickstart of a whole new fragrance family: the fougère, thanks to Paul Parquet's composition for Houbigant. Fougère Royale contained a staggering 10% coumarin of the finished formula! How one can dream a bit while reading Guy de Maupassant describing this fragrance as "prodigious evocation of forests, of lands, not via their flora but via their greenery"...

• The Fougere fragrance family

Fougère fragrances evoke the smell of ferns at least as we imagine them to be, as by themselves they don't have a particularly noticeable odour (Paul Parquet said that if they could, they'd smell of Fougere Royale). But the concept of a scent that is herbaceous, infused with aromatic lavender ~a popular material for both sexes at the end of the 19th century thanks to its propriety in the "clean" sense of the world~ and which leaves a malleable, soft, enveloping, yet discreet aura on the wearer was lacking: The era was still using the Victorian soliflores. Funnily enough, even those had their own categorisation; violets or roses for the respectable lady, jasmine and tuberose for the courtesan. Fougère scents were on the cusp between approved and revolutionary, creating a very desirable pull.
The other principle constituents in the accord are lavender and oakmoss: It was only natural; lavender by itself contains coumarin in its aromatic makeup. Thus the triad comprising the main accord of the rising fougère (i.e.lavender-oakmoss-coumarin, played together like a musical chord) made coumarin itself quite popular: many classic or influential masculine colognes owe their character to it, starting of course with Jicky and continuing with Azzaro pour Homme (1978), Fahrenheit by Dior (1988), Dolce & Gabanna pour homme (1994), and Gucci pour Homme (2003).
From there coumarin infiltrated its way into many modern fragrances belonging in other families. But it was its pliability and usefulness, like a trusty Swiss knife, which made it the perfumers' darling: Are there more contrasting fragrances than the icy aldehydic Rive Gauche (YSL 1970) and the intense floral Amarige (Givenchy 1991)? Perfumers tell me that coumarin ends up in some degree in 90% of all fragrances; and in concentrations exceeding 1% it accounts for over half of the fragrances in the market!!

• The odour profile of coumarin

Coumarin is a water-insoluble crystallized powder which has an odour that is pleasant, soft and warm, evoking cut grass or new mown hay, but it's more complex than that; it sometimes even veers into a smell of fresh paint! This is what gives Jicky its bracing almost "petrol" opening which alienates some people. Originally biosynthesized via hydroxylation, glycolisis and cinnamic acid cyclization, nowadays coumarin is produced via more sophisticated techniques.
Coumarin conjures warm notes of tobacco (useful in masculine formulae) and because it also has caramel overtones, alternatively it can be married to vanillic components (such as vanilla, benzoin or some of the other oriental balsams, such as Tolu balsam or Peru balsam, as well as ethylvanillin) in order to play down and sophisticate their foody aspects: see it in action in orientals such as the discontinued Venezia by Laura Biagotti, Lolita au Masculin(Lempicka) or Casmir by Chopard.
In dilution coumarin projects with soft hazelnut or almond facets underneath the hay, even licorice; smell Lolita Lempicka (1997). But in higher concentration it also has spicy fresh and herbaceous facets, no doubt reminiscent of its primary role in different grasses. In combination with vanillin and bergamot, we're veering into chypre territory: Elixir des Merveilles is a no man's land with its chypre tonalities and gourmand facets.
Its versatility and its ability to "fix" smell and make it last longer allows coumarin to enter amber or woody blends (witness Samsara or Vetiver by Guerlain) as well and even heighten the appeal of spicy materials: in fact it marries very well with cinnamon or clove. Pi by Givenchy is a sweet spicy woody with lots of tonka bean, or smell L de Lolita Lempicka by Maurice Roucel. Usually, indeed coumarin is mentioned in the form of tonka beans in the traditional lists of "notes"/pyramids for fragrances (see this Index for more ingredients contributing to which "note") but it can also hide underneath grassy notes, clover, lavender, or tobacco. Modern perfumers pair it with synthetic woody-amber notes such as Kephalis and Iso-E Super to surprising results. A wonderful material indeed!

• Fragrances featuring discernible amounts of coumarin

Addict (Dior)
A*men (Thierry Mugler)
Amarige (Gievnchy)
Angel ~all concentrations, esp. extrait de parfum(Thierry Mugler)
Angel Sunessence (T.Mugler)
Angel La Rose (T.Mugler)
Antidote (Victor & Rolf)
Azzaro pour Homme (Loris Azzaro)
Azzaro Elixir Bois Precieux (L.Azzaro)
Blue Jeans (Versace)
Bois des Iles (Chanel)
Brit (Burberry)
Chic for Men (Carolina Herrera)
Coco (Chanel)
Coco Mademoiselle (Chanel)
Contradiction (Calvin Klein)
Etoile de Rem (Reminiscence)
Fahrenheit (Dior)
Fieno (Santa Maria Novela)
Fougere Royal (Houbigant)
Florissa (Floris)
Gloria (Cacharel)
Jasmin Noir (Bulgari)
Jicky (Guerlain)
Joop! Homme (Joop)
Kouros (Yves Saint Laurent)
Lavande (Molinard)
L de Lolita Lempicka
Lolita Lempicka (L.Lempicka)
Le Male (Jean Paul Gaultier)
Musc (Molinard)
Navy (Lily Bermuda)
Pi (Givenchy)
Rive Gauche (YSL)
Samsara (Guerlain)
Tonka Imperiale (Guerlain)
Venezia (Laura Biagotti)
Versace pour Homme (Versace)

Related reading on Perfume Shrine: Perfumery Materials one by one

source of coumarin pic via The Health Nut Corner, ad for Houbigant via Punmiris and Jicky collage via Perfumesbighouse