Fragrances ChemistryVincent Médran-Navarrete, PhD
University of Antwerp17th 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.
Gi-vau-dan19%
Fir-menich
13 %
IFF12%Symrise
11%Takasag
o5%
Mane4%
Robertet
2%
Other33%
F&F market value (B$, 2014) : 16.5
Net sales (B$, 2014) :Givaudan : 4.8Firmenich : 3.3IFF : 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.
O
OOH
O
O
Ethylmaltolcaramel, cotton candy
Pomarosedry fruit, plum
(+)-cis-α-ironeiris, 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)
O
O
O
O
Olfactive game
Natural or synthetic ?
Who have the best nose ?
Structure of perfumes : the olfactive pyramid
Top< 1 h
Heart notes4 - 6 h
Base notes> 12 h
Fresh : orange, bergamot, lemon, mandarin, yuzuSpicy : lavender, thym, rosmary, pepper, paprika
Floral : rose, jasmin, yland-ylang, neroli, violetFruity : peach, raspberry, litchee, pinapple
Woody : vetiver, sandalwood, patchouli, cedarSweet : vanilla, tonka bean, caramel, chocolate
Structure of perfumes : the olfactive pyramid
www.olfatheque.com
The beginning of the modern perfumery
The coumarin
Tonka beansDipteryx odorata
Coumarin
O O
F. Wöhler, Liebigs Ann. Chem. 1856, 98, 66.
• 1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Wöhler ).
The beginning of the modern perfumery
The coumarin
Perkin condensation
Reimer-Tiemann reaction
OH
O
O
OO
OH
O
OHNaOAc O OOH
CHCl3 NaOH
Coumarin
F. Tiemann, H. Herfeld, Ber. Dtsch. Chem. Ges. 1877, 10, 283.W. H. Perkin, J. Chem. Soc. 1868, 21, 53.
• 1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Wöhler ).
• 1868 : first formal synthesis (W. H. Perkin).
The beginning of the modern perfumery
The coumarin
• 1856 : isolation by extraction of Tonka beans with 80 % ethanol (F. Wöhler ).
• 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
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.
OH(-)-(Z)-β-santalol20-25 % oil weight
East Indian Sandal (Santalum album)
Fragrance and chemistry for more sustainability
C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol
Fragrance and chemistry for more sustainability
C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol
Fragrance and chemistry for more sustainability
C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol
Fragrance and chemistry for more sustainability
C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol
Fragrance and chemistry for more sustainability
C. Fehr, I. Magpantay, J. Arpagaus, X. Marquet, M. Vuagnoux, Ang. Chem. 2009, 121, 7357.
Total synthesis of (-)-(Z)-β-santalol
Fragrance and chemistry for more sustainability
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
OH
The sandalwood osmophore
Fragrance and chemistry for more sustainability
The sandalwood osmophore
Fragrance and chemistry for more sustainability
terminal alcohol
(Z)-alkene
cyclopentyl ring
C5 side-chain
methyl group
OH
How to evaluate an odorant performance ?
Fragrance and chemistry for more sustainability
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
Fragrance and chemistry for more sustainability
OH
OH OH
Sandal Mysore Core (1978) Sandalwood, woody
th : 0.10 ng/LOV : 168,200
Ebanol (1986)Sandalwood, woody, musky
th : 0.21 ng/LOV : 211,760
Javanol (2000) Sandalwood, creamy, warm
th : 0.02 ng/LOV : 347,000
OOH
OH
Osyrol (1973) th : 49 ng/L
OV : 928
Sandalore (1976) th : 3 ng/LOV : 5,833
Protecting endangered wildlife : the Tonkin musk
Himalayan musk deer (protected specy)
O
Fragrance and chemistry for more sustainability
• 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
Fragrance and chemistry for more sustainability
• 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
Fragrance and chemistry for more sustainability
31 January 2013
Morecambe beach, Lancashire (UK)
9 lb ambergris chuck=
130,000 €
H
O
H
Formation of the ambergris odorant
(-)-Ambrox typicall ambergris
Fragrance and chemistry for more sustainability
H
H
OH
H
air, sunlight, waves1O2
(-)-Ambreinodorless
Freshly expelled ambergris
H
O
H
Formation of the ambergris odorant
Fragrance and chemistry for more sustainability
H
H
OH
H
air, sunlight, waves1O2
(-)-Ambreinodorless
Ambergris after maturation
(-)-Ambrox typicall ambergris
Fragrance and chemistry for more sustainability
OO
1. ClCH2CO2Et
2. H+ / heat, -CO2
1. HC(OEt)3, TsOH
2. ZnCl2, AcOEtO
ONa2S2O4
OH
H+
FSO3H O
H
H- 90 °C, 42 %
NO2
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
Fragrance and chemistry for more sustainability
OO
1. ClCH2CO2Et
2. H+ / heat, -CO2
1. HC(OEt)3, TsOH
2. ZnCl2, AcOEtO
ONa2S2O4
OH
H+
FSO3H O
H
H- 90 °C, 42 %
NO2
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
Fragrance and chemistry for more sustainability
OO
1. ClCH2CO2Et
2. H+ / heat, -CO2
1. HC(OEt)3, TsOH
2. ZnCl2, AcOEtO
ONa2S2O4
OH
H+
FSO3H O
H
H- 90 °C, 42 %
NO2
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
Fragrance and chemistry for more sustainability
OO
1. ClCH2CO2Et
2. H+ / heat, -CO2
1. HC(OEt)3, TsOH
2. ZnCl2, AcOEtO
ONa2S2O4
OH
H+
FSO3H O
H
H- 90 °C, 42 %
NO2
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
Fragrance and chemistry for more sustainability
OO
1. ClCH2CO2Et
2. H+ / heat, -CO2
1. HC(OEt)3, TsOH
2. ZnCl2, AcOEtO
ONa2S2O4
OH
H+
FSO3H O
H
H- 90 °C, 42 %
NO2
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
Fragrance and chemistry for more sustainability
Replacing pricy natural absolute with high fidelity synthetic blend
Sambac jasmine analyzed with Heaspace GC/MS
Molecules structure determination
Fragrance and chemistry for more sustainability
O
O
O
O
HO
OH
NH
OOO
O
CO2Me
O
CO2Me
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 %
Fragrance and chemistry for more sustainability
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 more sustainability
Fragrance and chemistry for creating not isolable smells
Diorissimo (Dior, 1956)
Raspberry ketonefruity, red berry
Ultrazur (Givaudan)ozonic, marine
O
HO
O
OH
Lyral (IFF)lily-of-the-valley, fresh, floral
O
O
O
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.
O
O
O
O
Givescone (Givaudan)
Fragrance and chemistry: improving customer safety
Replacing allergens with safe substitutes
Oakmoss O
O
OHHO
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 !
Bibliography
Where to buy perfumery ingredients ?
Thank you for your attention !!
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