Fragrances Chemistry

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 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.


• 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.

OH(-)-(Z)-β-santalol20-25 % 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

OH

The sandalwood osmophore


The sandalwood osmophore


terminal alcohol

(Z)-alkene

cyclopentyl ring

C5 side-chain

methyl group

OH

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


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


• 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 €

H

O

H

Formation of the ambergris odorant

(-)-Ambrox typicall ambergris


H

H

OH

H

air, sunlight, waves1O2

(-)-Ambreinodorless

Freshly expelled ambergris

H

O

H

Formation of the ambergris odorant


H

H

OH

H

air, sunlight, waves1O2

(-)-Ambreinodorless

Ambergris after maturation

(-)-Ambrox typicall ambergris


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


Replacing pricy natural absolute with high fidelity synthetic blend

Sambac jasmine analyzed with Heaspace GC/MS

Molecules structure determination


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 %


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 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 !!

Fragrances Chemistry

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