Introduction

Flavor and Fragrance
Chemistry
CHM 312, with Dr. Turk
From Lemons and Strawberries,
To Lavender and Rose...
From Sandalwood and Amber,
To Musk and Cedarwood...
TASTE &
SMELL
--- perhaps the most primitive and the most
powerful of our five senses.
In some cases, stripping nature of
chemicals that cause these
wonderful sensations for use in
household products, fine fragrances,
and foods depletes many of our
natural resources.
Did you know
the popular
odor of musk
originates
from a deer?
The continual harvest of natural resources to isolate the
chemicals responsible for their flavors and odors has driven
the PRICE of these ingredients UP!!
$$$
Chemical Synthesis provides a way to make
molecules with exactly the same sensory properties as
many natural products - not only can this make these
chemical ingredients cheaper, but…
This can help preserve our natural resources
Chemical Synthesis can also identify molecules
with new and interesting structures that have odor
qualities that can not be reproduced in nature!
Obtained from a
glandular secretion of
musk deer
(R)-Muscone
“very nice musky note,
rich and powerful musk”
Obtained via research
and chemical
synthesis
(R,Z)-Nirvanolide
“intense musky, fruity,
powdery odor”
1200 times stronger
than muscone
Heard of any of these
companies?
Abercrombie & Fitch
Banana Republic
Burberry
Calvin Klein:
Chanel
Cristian Dior
Estee Lauder
Giorgio Armani
Ralph Lauren
Tommy Hilfiger
Most of these fragrances were created by chemists and
perfumers or who work at LARGE fragrance companies
such as:
Givaudan, OH, IL, NJ, NY, KY + > 50 additional countries
2013 annual sales: $4905 (million) = 20.5% of total market share
Top 4
Firmenich, NJ, NY, Fl, MN, CA, MO + > 50 additional countries
2013 annual sales: $3314 (million) = 13.9% of total market share
International Flavors and Fragrances, NJ, NY, GA, Fl. TX + 30
additional countries
2013 annual sales: $2953 (million) = 12.4% of total market share
Symrise, NJ, OH, SC, NY + 34 additional countries
2013 annual sales: $2522 (million) = 10.5% of total market share
Other companies
in the top 10
Takasago, Wild Flavors, Mane SA, Sensient
Technologies, Frutarom, T. Hasegawa, Robertet
The top 10 F&F producers account for about 80%% of the entire
industry - leaving 20% to everyone else (Proctor and Gamble, Unilever
other smaller industries).
http://www.leffingwell.com/top_10.htm
How does this work in INDUSTRY?
There are hundreds of companies that create flavorings and
fragrance ingredients.
Their names never appear on the perfume bottle or the bag of
potato chips. All the fragrances sold by the Giorgio Armanis,
Vera Wangs, or Ralph Laurens, are not, in fact, created by Mr.
Armani or Ms. Wang or Mr. Lauren at all. The Perfume Brief
begins with a vision.
Say Miuccia Prada or Calvin Klein wants a fragrance…
“I want the smell of bitter apples frozen in a Chinese snow”
Or
“I want the scent of a young girl swimming in a dark Mediterranean sea...”
Marketing teams goes to work
FiFi Awards 2013
(Oscars of the fragrance industry)
Best New Female Fragrance
Dot, Marc Jacobs
Best New Male Fragrance
Spicebomb, Viktor & Rolf
Oliver Polge, IFF
Annie Buzantian, Firmenich
Regarding Perfumery, an article published on CNNMoney.com titled:
Six-Figured Jobs, Take 3
States: “A good nose and a good head for chemistry are two key traits for perfumers…”
“The field is small. There are only about 300 members of the American Society of Perfumers
and likely no more than 1,000 official perfumers worldwide.”
“A low headcount has helped keep the price for top talent high, said Steve Herman, a
chemist in the fragrance industry who teaches in a graduate cosmetic science program.”
“A junior perfumer may start out making $60,000… but perfumers who come up with
formulas for hit fragrances can easily command six figures.”
“Getting into the field usually requires a bachelor's degree in chemistry and time spent
working as a lab technician at a fragrance house. But there are some perfumers who don't
have college degrees… Once you prove you have a keen sense of smell, you may serve as
apprentice to a senior perfumer for five years, or the company may send you to perfumery
school…”
IFF
Beautiful, Estee Lauder
Euphoria, Calvin Klein
Happy, Clinique
Tresor, Lancome
Drakkar Noir, Guy Laroche
Polo Blue, Ralph Lauren
Very Irresistible L’Intense, Givenchy
Eternity Summer 11, Calvin Klein
Givaudan
Opium, Yves Saint Laurent
Poison, Christian Dior
Obsession, Calvin Klein
Angel, Thierry Mugler
Armani Code, Giorgio Armani
One Million, Paco Rabanne
Lola, Marc Jacobs
A Little Fragrance History...
1701
1759
1800
1833
1834
1837
1843
1853
1856
1859
1859-60
1863
1865
1866
1868
1869
1871
1874
1876
1875-77
1877
1878
1880
Observations that some flowers provided essential oil on steam distillation
Reaction of oil of amber with fuming nitric acid gave a musky odor
Investigations into ambra component chemistry
Empirical formula reported for anethole, borneol and camphor
Isolation of cinnamic aldehyde
Preparation of nitrobenzene
Isolation of benzaldehyde
Methyl salicylate determined as main component of wintergreen oil
Preparation of benzyl alcohol
Synthesis of aliphatic aldehydes
Synthesis of cinnamic aldehydes
Preparation of aldehydes from pyrolysis of calcium formate mixtures
Large-scale preparation of salicylic acid
Preparation of benzaldehyde
Determination of structure of benzene
Structure of cinnamic acid determined
Synthesis of coumarin
Discovery of heliotropin
Structure of heliotropin determined
Synthesis of vanillin from guaiacol
Discovery of phenylacetic aldehyde
Synthesis of cinnamic acid
Production of anisaldehyde from p-hydroxybenzaldehyde
Structure of terpin hydrate determined
Quinolines discovered
1884
1885
1888
1889
1890
1891
1893
1894
1898
1903
1904
1905
1905-08
1908
1913
1919
1921
1923
1926
1927
1928
Identification of d-limonene and dipentene
Structure of terpineol determined
Discovery of nitro musks
Discovery of citronellal
Synthesis of heliotropin from saffrole
Discovery of Rhodinol
Synthesis of ionone
Structure of alpha-pinene determined
Discovery of Musk Ketone
Discovery of methyl heptin carbonate and homologues
Fundamental work on aromaticity
Methyl nonyl acetic anhydride
Isolation of muscone
Glycidic method of synthesizing aldehydes
Synthesis of cinnamic alcohol
Hydroxycitronellal prepared and marketed
Discovery of gamma-undecalactone
Discovery of farnesol
Discovery of cyclamen aldehyde
Synthesis of linalool
‘Chanel No. 5’
Discovery of alpha amyl cinnamaldehyde
Discovery of nerolidol
Identification of muscone structure
Structural determination work on ambra, civet
Exaltone®
Ambrettolide®
Civetone®, Exaltolide®
1933
1934
1946
1947
1949
1953
1959
1962
1970
Structural determination of jasmone
Jasmone
Synthesis of muscone
Perfection of Wallach’s isoprene rule for terpenoids
Structural determination of irone
Ambrox®
New synthesis of linalool
cis-3-hexenol
Methyl dihydro-jasmonate
Damascones alpha and beta
Damascenones alpha and beta
Development of
NMR spectroscopy
A Brief History
of Fragrances
Early Raw Materials
Juniper Berries
Cinnamon
Frankincense
Myrrh
Calmus
Galangal
Way, way, way… WAY back then.
Perfume: “per fumus”,
meaning through smoke
7000 - 4000 BC
olive/sesame oil thought to have been mixed
with fragrant plants to create “perfumes”/ ointments
3000 BC
First written acknowledgment of perfumes
The presence of burned seeds, wood,
and flint at the Acheulian site of
Gesher Benot Ya`aqov in Israel is
suggestive of the control of fire by
humans nearly 790,000 years ago before the age of the Homo Sapien.
Science 30 April 2004:
Vol. 304 no. 5671 pp. 725-727
Retronasal perception of odors is a human
trait, which may have led to the evolutionary
flattening of our facial features
Cyprus Perfume Factory - 4000 years old (2000 BC)
3995-Square-Meter (about one acre) Perfume-Making Factory
Discovered by Italian archaeologists in 2007.
Over 60 stills, mixing bowl, funnels and perfume bottles
preserved under debris from earthquake in 1850BC.
The “Yellow Emperor”
Huang-ti Nei-ching
Book of Internal Medicine
2697 BC
Use of aromatic herbs
King Tutankhamun's (1332 BC - 1323 BC) tomb discovered 1922.
Pots filled with spices such as frankincense preserved in fat still
gave off a faint odor when opened in King Tutankhamen's tomb
3,000 years later
Egyptian Pharaoh Khufu (~ 2580 B.C.)
2650-2575 B.C. Frankincense, myrrh,
galbanum, cinnamon, cedarwood, juniper
berry and spikenard are all known to have
been used at some stage to preserve the
bodies of their royalty in preparation of the
after-life.
Great Pyramid (2700 BC)
Ebers Papyrus (1550 BC) - 110 page scroll - 20 meters long. Medical manuscript
of ancient Egypt purchased by Georg Ebers in 1873-1874.
The source of the papyrus is unknown, but it was said to have been found
between the legs of a mummy in the Theban necropolis.
For asthma - mix of herbs heated on a brick so the fumes could be inhaled
Temple of Edfu (237 BC - 57 BC)
Kyphi; although its recipe varies slightly
from temple to temple, the ingredients
always amount to sixteen (4x4) and
consist of raisins, burned resin, myrrh,
sweet rush, aspalathos, juniper,
cypress grass, honey and wine. Kyphi
was burnt nightly to please the Gods as
they began their journey into the
underworld and to ensure the safe
return of the sun God, Ra the next
morning.
Ancient Perfume Recipe
Temple of Edfu
Nero Claudis Caesar Augustus Germanicus (37-68), Roman Emperor
Frankincense
Myrrh
$100,000 to scent one party
1st Century AD, Romans used 3000 tonnes frankincense and 500 tones myrrh annualy
Among others...
Herodotus
Ovid
Pliny
important writers of classical antiquity (before 476 A.D.)
described formulations using multiple ingredients
Titus Lucretious Carus
(99 B.C. - 55 B.C.)
Barnes & Noble
•  pleasant smelling odorants were assumed to be of a smooth round geometry
•  harsh compounds possessed rough molecular surfaces
•  odor was elicited by molecules passing through slots of complementary shape
in the sensory organ (olfactory nerve)
‘lock and key’ principle
Napoleone di Buonaparte (1769 -1821)
Emperor of France
2 quarts of violet Cologne each week
60 bottles of jasmine extract per month
Jean-Francois Houbigant appointed
personal perfumer to Napoleon and
Empress Josephine
Also royal perfumer to the Tsar of Russia
1812 - Quelques Fleurs
(synthetic aldehyde C-12)
Bouquet de Napoléon, A. Rallet & Co.
Moscow, 1912
Ernest Beaux (1881-1961) - Russian - technical director at Rallet. Admired Houbigant,
and was known for mixing synthetic aldehydes with florals (rose, jasmine)
(1920) Gabrielle “Coco” Chanel + Grand Duke Dimitri Pavlovitch
Pavlovitch knew Rallet and Ernest, and while on vacation, she learned
of a perfumer named Ernest Beaux - who Pavlovitch suggested she
contact.
Chanel No. 5
Top note: Aldehydes, Bergamot
Lemon, Neroli
Middle note: Jasmine,
Lily of the Valley, Orris
Bottom Note: Vetiver,
Sandal, Vanilla, Amber
US Launch 1950
$200 / 0.5 oz bottle
Gisele Bündchen
Top note: Aldehydes, Bergamot
Lemon, Neroli
Middle note: Jasmine,
Lily of the Valley, Orris
Bottom Note: Vetiver,
Sandal, Vanilla, Amber
1832
1892
1900
1912
1926
1931
1937
1956
1981
1982
1998
Synthesis of Benzaldehyde
Allyl-sulfide identified in garlic
Saccharin first used as a sweetener
Maillard reaction first described
Furfuryl mercaptan identified in coffee
Amadori products recognized in the Maillard reaction
Sweetener cyclamate discovered
Use of GC to extract strawberry flavors
Aspartame gains FDA approval
Grapefruit mercaptan identified
Sucralose approved by the FDA
Flavor Chemistry
Did You
Know?????
Approximately 90% of what you perceive as
TASTE is actually due to the sense of SMELL???
What we call FLAVOR is actually a combination of TASTE and SMELL.
The Potato Chip
1960
Ready-salted cheese and onion
1970
Salt and vinegar
1980
Smoky bacon
Roast chicken
Roast ox
Bag of ready-salted and a bottle of red pop
1990
Roast beef and mustard
2000
Pack of Montery Jack kettle chips and a
mango and passionfruit smoothie
Sea salt and balsamic vinegar
Salsa and mesquite
Recent Literature
Journal of Agricultural and Food Chemistry
The Flavors and
Fragrances
Industry
Top 11 Total
Others
TOTAL
$23.9 billion industry
The Flavors and
Fragrances
Industry
Global Market for Flavors
(US$ Million)
Global Market for F&F
The Flavors and
Fragrances
Industry
Global Market for Fragrances
(US$ Million)
Global Market for F&F
A Note on Regulations
Fragrances: Raw materials and finished products
Geneva-based International Fragrance Association (IFRA)
US-founded Research Institute for Fragrance Materials (RIFM)
testing and monitoring of fragrance materials
A Note on Regulations
Flavors: More localized legislation (less international)
US-based Flavor and Extract Manufacturers Association (FEMA)
4000 materials that are Generally Recognized As Safe (GRAS)
FEMA GRAS - may be used at ‘set levels’, and may not be listed as
individual substances on ingredient list
Nature-identical synthetics
{
Europe: ‘contains flavoring’
US: ‘contains artificial flavoring’
Natural orPriceImitation
Availability of raw material
Permissibility under current legislation (toxicity test)
Problems of Using Natural Flavors
1) Many natural flavor have low intensity, it should be used at a high dosage which
results in an unsatisfactory texture and poor stability.
2) High concentrations of natural flavors is usually accompanied by significant changes in
the flavor profile.
3) Natural flavors exhibit variations in strength and quality.
4) The supply of natural materials may be uncertain.
5) Most natural flavors are unstable and undergo changes during post-harvest
handling, processing or storage.
6) Many natural products contain enzyme systems which may result in decomposition
and/or the formation of off-notes.
7) The toxicity of many natural products has yet to be established.
Natural or Imitation
Disadvantages of Using Imitation Flavors
1) Original natural flavor is more subtle - imitation flavor sometimes
described as “chemical”
2) Difficulties in “labeling”
3) Imitation flavor generally require the use of either a solvent or a carrier
4) Restriction by legislation
5) Problems with texture in the end product