Fragrances Chemistry

Fragrances Chemistry
Vincent Médran-Navarrete, PhD
University of Antwerp
17th December 2015

Introduction – History
From the Latin « per fumum » (« through the fumes ») because ancient
civilizations initially produced perfumes with resins fumigation (incense,
myrrh, benzoin).
Myrrh nuggets

«toilette »
Introduction – Perfume grades
20-30 %10-20 %
8-10%
Eau de toilette
Eau de parfum Parfum

Introduction – The perfumes industry
Few perfumes are created by the luxury brands themselves. In France, only the
« Grandes Maisons » such as DIOR, CHANEL, GUERLAIN, HERMES, PATOU and
CARTIER have in-house master perfumers (the « nose ») who creates the
fragrances.
François Demachy
(Dior)
Olivier Polge
(Chanel)
Thierry Wasser
(Guerlain)
Mathilde Laurent
(Cartier)
Most of the time, the luxury brands call for a tender within F&F manufacturing
companies which create the fragrances for them.

Givaudan
20%
Firmenich
13 %
IFF
12%
Symrise
11%
Takasago
5%
Mane
4%
Robertet
2%
Other
33%
F&F market value (B$, 2014) : 16.5
Net sales (B$, 2014) :
Givaudan : 4.8
Firmenich : 3.3
IFF : 3.1
Source : Leffingwell & Associates
Market shares of the top F&F companies (2014)
Introduction – The Flavor and Fragrance market

Introduction – Perfumes bestseller
Angel (Thierry Mugler, 1992)
Created by Firmenich
La Vie est Belle (Lancôme, 2012)
Created by IFF
How do F&F companies create bestsellers perfumes ?
Because the R&D chemists develop innovative and trendsetting
ingredients that boost perfumes sales.
Ethylmaltol
caramel, cotton candy
Pomarose
dry fruit, plum
(+)-cis-α-irone
iris, violet
One Million (Paco Rabanne, 2008)
Created by Givaudan

Note : one ingredient with one characteristic smell (e.g. : cinnamon = spicy note)
Accord : combinaison of 2 notes (or more) that creates a new smell, different from each individual
notes. With more than 4,000 raw material available, the possibility are almost infinite !
Perfumes organ : perfumer instrument
The perfumer symphony
Note A Note BAccord
Accord « Fougère » : lavender,
bergamot, oakmoos, coumarin
(e.g. : L’Homme, YSL, 2006)

Natural : from natural resource (flower, wood, animal…) ; generally a complex mixture (e.g. :
Madagascar vanilla absolute).
Synthetic : the natural molecule is reproduced with organic synthesis. It is a chemically defined
compound (e.g. : vaniline) often more stable and cheaper than natural ingredients.
Artificial : the molecule does not exist in the nature (e.g. : ethylvaniline). Artificial materials
allow more creativity to perfumers and provide them access to smells that cannot be isolated
(e.g. : marine notes, leather notes…).
The perfumer palette
Calone (Pfizer, 1966) Safralein (Givaudan)

Olfactive game
Natural or
synthetic ?
Who have the
best nose ?

Structure of perfumes : the olfactive pyramid
Top
< 1 h
Heart notes
4 - 6 h
Base notes
> 12 h
Fresh : orange, bergamot, lemon, mandarin, yuzu
Spicy : lavender, thym, rosmary, pepper, paprika
Floral : rose, jasmin, yland-ylang, neroli, violet
Fruity : peach, raspberry, litchee, pinapple
Woody : vetiver, sandalwood, patchouli, cedar
Sweet : vanilla, tonka bean, caramel, chocolate

Structure of perfumes : the olfactive pyramid
www.olfatheque.com

The beginning of the modern perfumery
The coumarin
Tonka beans
Dipteryx odorata
Coumarin
F. Wöhler, Liebigs Ann. Chem. 1856, 98, 66.
• 1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Wöhler ).

The coumarin
Perkin
condensation
Reimer-Tiemann
reaction
Coumarin
F. Tiemann, H. Herfeld, Ber. Dtsch. Chem. Ges. 1877, 10, 283.
W. H. Perkin, J. Chem. Soc. 1868, 21, 53.
• 1868 : first formal synthesis (W. H. Perkin).

The coumarin
• 1868 : first formal synthesis (W. H. Perkin).
• 1884 : first synthetic molecule to be used in a perfume (Fougère Royale).
Fougère Royale
(Houbigant, 1884)
Today, most of fragrances contains synthetic ingredients
but not always for economical reasons !!

Fragrance and chemistry for more sustainability
Preservating natural resource : the sandalwood oil
East Indian Sandal
(Santalum album)
• One of the oldest perfumery ingredients (used since 4,000 years).
• Obtained by steam distillation of +30-y.o. wood (yield : 6 %).
Sandalwood

Preservating natural resource : the sandalwood oil
• One of the oldest perfumery ingredients (used since 4,000 years).
• Obtained by steam distillation of +30-y.o. wood (yield : 6 %).
• Overharversting endangered the sandal tree (2004 IUCN Red List).
High need for synthetic substitute ingredients.
(-)-(Z)-β-santalol
20-25 % oil weight
East Indian Sandal
(Santalum album)

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Elegant but not
applicable to
industrial scale
Total synthesis of (-)-(Z)-β-santalol

The sandalwood osmophore

The sandalwood osmophore
terminal alcohol
(Z)-alkene
cyclopentyl ring
C5 side-chain
methyl group

How to evaluate an odorant performance ?
Odor Value (OV)
Vapor pressure (ng/L air)
Threshold concentration (ng/L air)
=
Threshold : lowest perceptible concentration in the air (ng/L)
G. Frater, J. A. Bajgrowicz, P. Kraft, Tetrahedron 1998, 54, 7633.
High OV = powerful smell

Design of synthetic sandalwood odorants
Sandal Mysore Core (1978)
Sandalwood, woody
th : 0.10 ng/L
OV : 168,200
Ebanol (1986)
Sandalwood, woody, musky
th : 0.21 ng/L
OV : 211,760
Javanol (2000)
Sandalwood, creamy, warm
th : 0.02 ng/L
OV : 347,000
Osyrol (1973)
th : 49 ng/L
OV : 928
Sandalore (1976)
th : 3 ng/L
OV : 5,833

Protecting endangered wildlife : the Tonkin musk
Himalayan musk deer
(protected specy)
• One of the pricest perfumery ingredients (60,000 €/kg).
• Illegally extracted from the musk deer pods (poaching).
• Base note with excellent fixative properties.
• Provides warmth, sensuality and tail to perfumes.
Muscs Koublaï Khan
(Serge Lutens, 1998)
(-)-(R)-Muscone

Developping substitute for extremely rare ingredients : the ambergris
Sperm whale
• Smells woody, camphoraceous, oceanic, musky.
• One of the most expensive and rarest perfumery ingredients (50,000€/kg).
• Excellent fixative properties (last several months on a blotter).
• Results from from digestive pathology of sperm whales (c.a. 1 %). A “whale
vomit” that turns into “floating gold”.
Ambergris chunk

The luckiest british guy of the year 2013
31 January 2013
Morecambe beach, Lancashire (UK)
9 lb ambergris chuck
=
130,000 €

Formation of the ambergris odorant
(-)-Ambrox
typicall ambergris
air, sunlight, waves
1O2
(-)-Ambrein
odorless
Freshly expelled
ambergris

Formation of the ambergris odorant
air, sunlight, waves
1O2
(-)-Ambrein
odorless
Ambergris after
maturation
(-)-Ambrox
typicall ambergris

D. Helmlinger, to Givaudan, Eur. Pat. Appl. EP 0.585.828, 1994 (Chem. Abstr. 1994, 121, 34867).
R. L. Snowden, J.-C. Eichenberger, S. M. Linder, P. Sonnay, C. Vial, K. H. Schulte-Elte, J. Org. Chem. 1992, 57, 955.
(±)-Ambrox
β-Ionone
Hemisynthesis of (±)-Ambrox : from violet to ambergris

Replacing pricy natural absolute with high fidelity synthetic blend
8 millions hand-picked jasmine flowers (1,000 kg)
2.3 kg of jasmine concrete
1 kg jasmine absolute (yield : 0.1 %)
Price : 15,000 € / kg

Replacing pricy natural absolute with high fidelity synthetic blend
Sambac jasmine analyzed with
Heaspace GC/MS
Molecules structure
determination

Benzyl acetate
34 %
Benzyl benzoate
24 %
Benzyl alcohol
5 %
Linalool
8 %
1H-indole
2.5 %
cis-Jasmone
3 %
(-)-δ-jasmolactone
1.5 %
(-)-Methyl jasmonate
1.7 %
(+)-epi-Methyl jasmonate
0.2 %

Replacing pricy natural absolute with high fidelity synthetic blend : Sampaquita Jasmine
Sambac jasmine analyzed with
Heaspace GC/MS
Molecules structure
determination
Synthetic chemistry

Fragrance and chemistry for creating not isolable smells
Diorissimo
(Dior, 1956)
Raspberry ketone
fruity, red berry
Ultrazur (Givaudan)
ozonic, marine
Lyral (IFF)
lily-of-the-valley, fresh, floral

Fragrance and chemistry: the embellisher notes
White musks : a cocoon of softness
Cosmone
(Givaudan)
Galaxolide
(IFF)
White musk are base note that round up and soften the whole
composition. They bring confort and increase the longevity of
the perfumes.
Givescone
(Givaudan)

Fragrance and chemistry: improving customer safety
Replacing allergens with safe substitutes
Oakmoss
Veramoss (IFF)
Oakmoos is the main constituent of the
very popular Chypre accord with patchouli,
labdanum, rose and bergamot.
But natural oakmoos contains strong
allergens.
Chypre (Coty, 1917)

Conclusion
Synthetic chemistry brings more creativity to perfumer and provides
affordable and safe ingredients.
Naturals and synthetics should not be opposed as
all matter is chemical  !

Where to buy perfumery ingredients ?

Thank you for your attention !!

Fragrances Chemistry

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