Transcript Research Proposals

Chemistry of
Fragrance Ingredients
Dr. William L. Schreiber
Chemlumina LLC
Monmouth University
Presented at Fairleigh Dickenson University
November 7, 2006
To be discussed
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What is a perfume?
History
Natural Ingredients
Synthetic Ingredients
Chemical Process Examples
Research on New Synthetics
The Science of Olfaction
What Are Perfumes?
Mixtures that are created for use in a wide
variety of applications:
expensive couturier perfumes, cosmetics,
personal grooming products, laundry products,
household cleaning products, air fresheners,
candles, etc., etc., etc..
From a palette of several thousand
materials, most of which are manufactured by
chemical processing methods.
History of Perfumes
5000 BC –
Egyptian First Dynasty – earliest evidence
3000 BC – Mesopotamia: extraction pots, early apparatus
1400 BC –
Book of Exodus “anointing with oils”
370 BCE – Theophrastus writings on use of oils to make
fragrances longer lasting.
800 AD – Alembic distillation apparatus – Jabir ibn Hayyan
1200 AD –
Essential oils produced in pharmacies
1600 AD – Quality of many natural extracts established
1860 AD –
1900 AD –
First synthetics (naturally occuring materials)
First non-natural synthetics (ionones, nitromusks)
Alembic Distillation Appratus
What are Fragrance Ingredients?
• Odorants, Diluents and Fixatives
• Naturals and Synthetics
• Chemicals having 6 – 18 carbon atoms
(mostly), and usually one oxygenated
functional group. There are also some
multi-functional materials as well as a
few sulfur- and nitrogen-containing
chemical compound.
What are Fragrance Ingredients?
alcohols
R
OH
OH
phenolics
aldehydes
R
CHO
O
ketones
R
R
O
esters
olefins
R
O
O
R
O
mercaptans
amines
R
SH
N
Performance in Use
• Volatility
– Function of molecular weight (how many
carbons) and chemical type.
• Stability
– Function of chemical type and use condition
(acidity, alkalinity, oxidizing, open, closed).
• Odor Threshold and dose/response
– Function of chemical structure (molecular
shape and chemical type).
Natural Ingredients
• Mostly of vegetative origin, a few from
animal secretions – largely replaced.
• Any part of a plant may be used:
flowers, fruits, leaves, twigs, roots, wood.
• Synthetics have long overtaken naturals
in volume of use.
• Naturals still very valuable and provide
odor reference points for all materials.
Types of Naturals
Concretes –
extracts with solvent removed
Absolutes –
concretes re-dissolved and
filtered to remove waxes, etc.
Essential oils –
distillates, often with steam
Narcisse Concrete
Rose
Most important constituents:
OH
OH
citronellol
linalool
O
OH
b-phenethyl alcohol
b-damascenone
Jasmine
Most important constituents
O
O
COOCH3
cis-jasmone
methyl jasmonate
N
H
indole
Patchouli
Most important constituents:
HO
HO
HO
tricyclic sesquiterpene alcohols
Sandalwood
• Alpha Santalol:
OH
• Beta Santalol:
OH
First Synthetics
CH3O
O
O
HO
O
coumarin
vanillin
NO2
O
O2N
methyl ionone gamma
NO2
musk xylol
Synthesis of Vanillin
CH3O
CH3O
OH-
HO
HO
isoeugenol
eugenol
(from clove oil)
CrVI or MnVII
CH3O
HO
O
Synthesis of Coumarin
CHO
+
OH
salicylaldehyde
O
O
O
KOAc
acetic
anhydride
(Perkin condensation)
O
O
Synthesis of Ionones
O
O
O
+
OH-
2-butanone
citral
H3PO4
O
alpha-irone
O
"gamma methyl ionone"
Terpene Alcohols from -Pinene
HCl
Cl
beta-pinene
3
myrcene
sodium
acetate
OH-
H2
OH
citronellol
OH
OAc
geranyl acetate
Terpene Alcohols from -Pinene
OOH
O2
H2
alpha-pinene
H2
3
OH
OH
OH

geraniol
linalool
More Products from -Pinene via
Myrcene
HO
HO
*
CHO
CHO
(acrolein)
Lyral
O
*
O
O
H+
Iso E Super
O
CHO
+
* Diels - Alder Reactions
Sandalwood
“Molecular Engineering”
• Alpha Santalol:
OH
• Beta Santalol:
OH
Synthetic Sandalwoods
O
peracetic
acid
alpha-pinene
CHO
ZnCl2
campholenic aldehyde
O
CHO
O
O
OH
OH
H2
Sandalore
Bacdanol
Musks
O
O
O
muscone
muskalactone
O
O2N
O
NO2
musk ketone
Galaxolide
Galaxolide Synthesis
H
+
t-amylene
a-methylstyrene
O
(propylene
oxide)
(CH2O)n, H+
O
(paraformaldehyde)
OH
Newer Musk Synthesis
O
+
OH
peroxide
catalyst
O
O
OH
H+
allyl alcohol
cyclododecanone
H2O2
O O
H2
OH
O O
O O
Cu
catalyst
Muskalactone
Globalide
Habanolide
Research and Development
• Analytical
– Application of new gc methods (head space
with spme)
– Use of more sensitive and better
computerized instrumentation: gc-ms, nmr, ftir.
• Live flowers – above methods used to
analyze odors of flowers before picking.
• New extraction methods for naturals:
supercritical CO2
Synthetic Research
Considerations:
• Structure – relationship to materials of
known value – natural or synthetic
• Raw materials
• Process
(often a combination of all three)
Synthetic Research
Practical only for largest companies.
• Hundreds of materials synthesized
each year for evaluation.
• In-depth evaluation must include
testing in fragrances and in
applications.
• Decision to develop cannot be taken
lightly.
Development of New Synthetics
• Processes must be very well worked out
in laboratory, pilot plant and factory.
• Best economics, safety and workplace
hygiene.
• Testing is required to meet industry
safety standards and international PMN
requirements for all new chemicals.
• Cost to register new ingredients
worldwide is well over $300,000.
How We Smell
Recent Developments
• 1991 – Richard Axel and Linda Buck
discover a family of genes that appear to be
responsible for olfactory receptors.
(received Nobel Prize – 2005)
• 1998 – Stuart Firestein expresses a receptor
from one of those genes and shows it
responds to different odorants.
• 2000 – Linda Buck shows that odor
perception is based on combinatorial
interaction of odorants with receptors.
A Code in the Nose
Combinatorial Detection
A
B
C
D
E
F
1






2






3






Receptors
4 5 6 7 8 9
   
   
    
    
   
    
350 Receptors: 2350 =
2.3X10105 Combinations
10 ….






 = Unactivated
 = Activated
In Conclusion…
• Fragrance ingredients are a complex part
of a the even more complex world of
perfumes. Understanding what they are,
where they come from and what they do
Thank
you
for
the
opportunity
to
is the key to making better smelling and
participate
in your
class this
better performing
fragrances.
evening.