Fragrances Chemistry

Vincent Mdran-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
Introduction Perfume grades

10-20 % 20-30 %
8-10%
Eau de parfum Parfum
toilette
Eau de toilette
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.

Franois Demachy Olivier Polge Thierry Wasser Mathilde Laurent

(Dior) (Chanel) (Guerlain) (Cartier)

Most of the time, the luxury brands call for a tender within F&F manufacturing
companies which create the fragrances for them.
 Introduction The Flavor and Fragrance market

Market shares of the top F&F companies (2014)

Givaudan
F&F market value (B$, 2014) : 16.5
Other 20%
33% Net sales (B$, 2014) :
Givaudan : 4.8
Firmenich
13 % Firmenich : 3.3
IFF : 3.1
Robertet
2%

Mane
IFF
4%
Takasago 12%
Symrise
5% 11%
Source : Leffingwell & Associates
 Introduction Perfumes bestseller

(+)-cis--irone
Pomarose iris, violet
dry fruit, plum
Ethylmaltol
caramel, cotton candy

One Million (Paco Rabanne, 2008) La Vie est Belle (Lancme, 2012)
Created by Givaudan Created by IFF

Angel (Thierry Mugler, 1992)

Created by Firmenich How do F&F companies create bestsellers perfumes ?
Because the R&D chemists develop innovative and trendsetting
ingredients that boost perfumes sales.
 The perfumer symphony

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

Note A Accord Note B

Accord Fougre : lavender,

bergamot, oakmoos, coumarin
(e.g. : LHomme, YSL, 2006)
 The perfumer palette

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).

Calone (Pfizer, 1966) Safralein (Givaudan)

Olfactive game

Natural or
synthetic ?

Who have the

best nose ?
Structure of perfumes : the olfactive pyramid

Fresh : orange, bergamot, lemon, mandarin, yuzu

<1h Spicy : lavender, thym, rosmary, pepper, paprika

Floral : rose, jasmin, yland-ylang, neroli, violet

4-6h Fruity : peach, raspberry, litchee, pinapple

Woody : vetiver, sandalwood, patchouli, cedar

> 12 h Sweet : vanilla, tonka bean, caramel, chocolate
 Structure of perfumes : the olfactive pyramid

www.olfatheque.com
 The beginning of the modern perfumery

The coumarin

1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Whler ).

Coumarin
Tonka beans
Dipteryx odorata

F. Whler, Liebigs Ann. Chem. 1856, 98, 66.

 The beginning of the modern perfumery

The coumarin

1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Whler ).

1868 : first formal synthesis (W. H. Perkin).

Reimer-Tiemann Perkin Coumarin

reaction condensation

F. Tiemann, H. Herfeld, Ber. Dtsch. Chem. Ges. 1877, 10, 283.

W. H. Perkin, J. Chem. Soc. 1868, 21, 53.
 The beginning of the modern perfumery

The coumarin

1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Whler ).

1868 : first formal synthesis (W. H. Perkin).
1884 : first synthetic molecule to be used in a perfume (Fougre Royale).

Today, most of fragrances contains synthetic ingredients

but not always for economical reasons !!

Fougre Royale
(Houbigant, 1884)
 Fragrance and chemistry for more sustainability

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 %).

East Indian Sandal

(Santalum album)
Sandalwood
 Fragrance and chemistry for more sustainability

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.

East Indian Sandal

(Santalum album)
(-)-(Z)--santalol
20-25 % oil weight
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

Total synthesis of (-)-(Z)--santalol

Elegant but not

applicable to
industrial scale

C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
 Fragrance and chemistry for more sustainability

The sandalwood osmophore

 Fragrance and chemistry for more sustainability

The sandalwood osmophore

(Z)-alkene

cyclopentyl ring methyl group

C5 side-chain terminal alcohol

 Fragrance and chemistry for more sustainability

How to evaluate an odorant performance ?

Threshold : lowest perceptible concentration in the air (ng/L)

Vapor pressure (ng/L air)

Odor Value (OV) =
Threshold concentration (ng/L air)

High OV = powerful smell

G. Frater, J. A. Bajgrowicz, P. Kraft, Tetrahedron 1998, 54, 7633.

 Fragrance and chemistry for more sustainability

Design of synthetic sandalwood odorants

Osyrol (1973) Sandalore (1976) Sandal Mysore Core (1978)

th : 49 ng/L th : 3 ng/L Sandalwood, woody
OV : 928 OV : 5,833 th : 0.10 ng/L
OV : 168,200

Ebanol (1986) Javanol (2000)

Sandalwood, woody, musky Sandalwood, creamy, warm
th : 0.21 ng/L th : 0.02 ng/L
OV : 211,760 OV : 347,000
 Fragrance and chemistry for more sustainability

Protecting endangered wildlife : the Tonkin musk

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.

Himalayan musk deer

(protected specy)
(-)-(R)-Muscone
Muscs Koubla Khan
(Serge Lutens, 1998)
 Fragrance and chemistry for more sustainability

Developping substitute for extremely rare ingredients : the ambergris

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.

Sperm whale

Ambergris chunk
 Fragrance and chemistry for more sustainability

The luckiest british guy of the year 2013

31 January 2013
Morecambe beach, Lancashire (UK)

9 lb ambergris chuck
=
130,000
 Fragrance and chemistry for more sustainability

Formation of the ambergris odorant

air, sunlight, waves

1O
2

Freshly expelled
ambergris
(-)-Ambrein (-)-Ambrox
odorless typicall ambergris
 Fragrance and chemistry for more sustainability

Formation of the ambergris odorant

air, sunlight, waves

1O
2

Ambergris after
maturation
(-)-Ambrein (-)-Ambrox
odorless typicall ambergris
 Fragrance and chemistry for more sustainability

Hemisynthesis of ()-Ambrox : from violet to ambergris

-Ionone

()-Ambrox

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.
 Fragrance and chemistry for more sustainability

Hemisynthesis of ()-Ambrox : from violet to ambergris

-Ionone

()-Ambrox

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.
 Fragrance and chemistry for more sustainability

Hemisynthesis of ()-Ambrox : from violet to ambergris

-Ionone

()-Ambrox

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.
 Fragrance and chemistry for more sustainability

Hemisynthesis of ()-Ambrox : from violet to ambergris

-Ionone

()-Ambrox

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.
 Fragrance and chemistry for more sustainability

Hemisynthesis of ()-Ambrox : from violet to ambergris

-Ionone

()-Ambrox

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.
 Fragrance and chemistry for more sustainability

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
 Fragrance and chemistry for more sustainability

Replacing pricy natural absolute with high fidelity synthetic blend

Molecules structure
Sambac jasmine analyzed with determination
Heaspace GC/MS
Fragrance and chemistry for more sustainability

Benzyl acetate Benzyl benzoate Benzyl alcohol Linalool

34 % 24 % 5% 8%

1H-indole cis-Jasmone (-)--jasmolactone

2.5 % 3% 1.5 %

(-)-Methyl jasmonate (+)-epi-Methyl jasmonate

1.7 % 0.2 %
 Fragrance and chemistry for more sustainability

Replacing pricy natural absolute with high fidelity synthetic blend : Sampaquita Jasmine

Molecules structure Synthetic chemistry

Sambac jasmine analyzed with determination
Heaspace GC/MS
 Fragrance and chemistry for creating not isolable smells

Raspberry ketone
4-(4-hydroxyphenyl)
butan-2-one

Lyral (IFF) Ultrazur (Givaudan)

lily-of-the-valley, fresh, floral ozonic, marine
Diorissimo
(Dior, 1956)
 Fragrance and chemistry: the embellisher notes

White musks : a cocoon of softness

Cosmone Galaxolide Givescone

(Givaudan) (IFF) (Givaudan)

White musk are base note that round up and soften the whole
composition. They bring confort and increase the longevity of
the perfumes.
 Fragrance and chemistry: improving customer safety

Replacing allergens with safe substitutes

Oakmoos is the main constituent of the

very popular Chypre accord with patchouli,
labdanum, rose and bergamot.
But natural oakmoos contains strong
allergens.

Oakmoss
Chypre (Coty, 1917)

Veramoss (IFF)
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 !
Bibliography
Where to buy perfumery ingredients ?
Thank you for your attention !!