Perfumery

as a
Science

Steve Herman
FRAGRANCE
CREATION
VOLATILITY

For a molecule
To have odor,
MW<300 for
appreciable
vapor pressure
at RT
 BASIC COMPOSITION
FRAGRANCE TRIANGLE
Jean Carles:
25% Evaluate volatility
TOP Construct accords
Build from
25% MIDDLE bottom up
50% BOTTOM
CARLES BASE ACCORD
Oakmoss 9 8 7 6 5
Ambergris 1 2 3 4 5

Selects 6:4, needed musk

for chypre character:
6 Oakmoss
4 Ambergris
1 Musk Ketone
ADD MIDDLE

Adds floral and

animal notes:

3 Absolute Rose
1 Absolute Civit 10%
6 Oakmoss
4 Ambergris
1 Musk Ketone
 TOP ADDED

Pleasant, highly volatile

notes for sparkle:
4 Sweet Orange Oil
1 Bergamot
3 Absolute Rose
1 Absolute Civit 10%
6 Oakmoss
4 Ambergris
1 Musk Ketone
FRAGRANCE
CHEMICALS
 CHEMICAL TYPES
• Alcohols
• Aldehydes & Ketones
• Aliphatic & Aromatic Esters
• Nitriles
• Ethers
• Lactones
• Heterocyclics
• Terpenes
ALCOHOLS
R-OH
Aliphatic
OH

Aromatic
 ALDEHYDES & KETONES

H
C=O Aldehyde
R
R’
C=O
R Ketone
TERPENES #1
Isoprene Units
Joined Head To Tail

(C5H8)n
C
I
C=C-C=C
 TERPENES #2

n Name Formula
2 Monoterpene C10H16
3 Sesquiterpene C15H24
4 Diterpene C20H32
6 Triterpene C30H48
8 Tetraterpene C40H64
 ACYCLIC TERPENES

β-Myrcene
MONOCYCLIC TERPENES

Limonene
BICYCLIC
TERPENES

Pinene
SESQUITERPENE

γ-Bisabolene
 NITRILES

R-C=N Aliphatic

C=N

Aromatic
BASIC HETEROCYCLIC STRUCTURES

N O S
+ +

N O S
H
HETEROCYCLICS

N
H

Indole
 LACTONE
A Cyclic Ester
γ or δ Hydroxy Acid forms
5 or 6 member ring by
intramolecular
esterfication
-
RCHCH2CH2COO Na +
I
OH
LACTONES

O O

Coumarin
 NITROMUSKS

C((CH)3)3 C((CH)3)3
NO2 NO2 NO2 NO2

NO2
CH3 CH3 CH3 CH3
NO2 C=O
I
CH3

Musk Xylene Musk Ketone

POLYCYCLIC MUSKS

Galaxalide
 FRAGRANCE DILUENTS 1
CH3CHCH2-O-CH2CHCH 3
I I
OH 0H

Dipropylene Glycol (DPG)

CH3CHCH2OH
I
OH
Propylene Glycol (PG)
FRAGRANCE DILUENTS 2
HOCH2CH2CHCH3 Butylene Glycol
I
OH

CH3
I
CH3CCH2CHCH3
Hexylene Glycol
I I
OH OH
 SCHIFF BASE #1
Aldehyde + Amine
COOCH3
H 2N
CHO +

OH
Methyl
Hydroxy-
Anthranilate
Citronellal
SCHIFF BASE #2

COOCH3

CH=N + H 2O

OH
Aurantiol
CHEMICAL REACTIONS

HELPFUL REACTIONS
Part of the natural
maturing process
HARMFUL REACTIONS
Occur in isolated
perfume oils or in reaction
with base environment
STORAGE EFFECTS
• Elevated Temperatures
• UV Radiation
• Moisture
• Oxidation

Accelerate change
or deterioration
 AUTOOXIDATION
CHO COOH

Benzaldehyde Benzoic
Acid
 POLYMERIZATION
Aldehydes can
Solidify
OH
CH2CHO I
CH2CH-CHCHO
2

Phenylacetaldehyde
 HEMIACETALS
Aldehyde/Ketone + Alcohol
O OH
II I I
C +- C- OH C
O
Loose, reversible C
aging
hydroalcoholics
 ESTER HYDROLYSIS
O

OH
O
-OH

Benzyl Benzyl
Acetate Alcohol
 LACTONE HYDROLYSIS
O OH
-OH

O O
HO

Epsilon 6-Hydroxy
Hexalactone Hexanoic Acid
 FRAGRANCE
APPLICATIONS-
PERSONAL
CARE
 CHEMICAL EXAMPLES 1
CH2CH2OH
PEA
. β-Pinene
 CHEMICAL EXAMPLES 2
Hydroxycitronellal
OH CH3
I I
CH3CCH2CH2CH2CHCH2CH
I II
CH3 O
CH3
HOCH2CH2CH
Amyl Alcohol CH3
SOLUBILITY PARAMETER
Measure of all the
cohesive forces in
a molecule

Refinement of
“polar”
“nonpolar”
division
 CLOG P

Calculated
LOGarithm of the
octanol/water
Partition
Coefficient

Trinh et al 5,783,544, 1998

 SMILES

SIMPLIFIED MOLECULAR
INPUT LINE ENTRY
SYSTEM

Allows entry of chemical structures into

computer programs to predict
properties
 EXAMPLE SMILES
Case Important-
Aliphatic Upper Case
Aromatic Lower Case
Hydrogen Not Included
SINGLE BOND C-C
DOUBLE BOND C=C
TRIPLE BOND C#C
Rings- # at start and end
e.g. c1ccccc1Br is Bromobenzene
 CLOG P VANILLIN
SMILES: COc1cc(C=O)ccc1O

HO

O CH
H3C
O
CONSEQUENCE

Fragrance will partition

in phases of finished
product
FUNCTIONAL FRAGRANCE

• Economics
• Stability
• Translation
TEA-STEARATE EMULSION
Air
CH2CH2OH

PEA Stearyl alcohol

Amyl alcohol
O

TEA-Stearate
O
Hydroxycitronellal
Pinene
SURFACTANTS
More stable than
emulsions, but
viscosity more
important, often
color problems
MICELLE EFFECTS
Water-Micelle
Interface

Between
Surfactant
Molecules

Core of
Micelle
SURFACTANT VISCOSITY
Water 67.0
Sodium Laureth Sulfate (A) 18.0
Cocamidopropyl Betaine (B) 15.0

1. Unperfumed
2. 2% Hydroxycitronellal
3. 2% Phenylethyl Alcohol

A. Standapol ES-2 (COGNIS)

B. Velvetex BK-35 (COGNIS)
 VISCOSITY
1,000

800

600

400

200

1 2 3
FRAGRANCE
APPLICATIONS-
HOUSEHOLD
PRODUCTS
Wt Loss
EVAPORATION CURVE

Days
Typical Fragrance Evaporation Curve
Weight
FREE EVAPORATION

1 2 3 4

Time
 LINEAR FRAGRANCE

4
Weight

3
2
1

Time
 BLEACH
Bleach unstable, affected by
fragrance, solubilizer,
oxygen, temperature-
must test chlorine and fragrance.
 DECOMPOSITION AT 100°F
5.6
5.4
5.2
5.0
4.8
% NaOCl

4.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
3.0
2.8
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Days
DOWFAX STRUCTURE
SO3-X+ SO3-X+

R
 TITRATION
0.1 N Sodium
Thiosulfate

Titrate
until
clear
Bleach
Stirring Test
Bar Mixture
Magnetic
Stirrer
 MASKING/MALODOR

Foul odors from

bacterial
decomposition
or unpleasant
molecules
FAMOUS MALODORS
putrescine

cadaverine

spermidine

spermine
 SKUNK ODOR
H CH2SH
C=C E-2-buten-1-thiol
CH3 H 38-44%

3-methyl-1-butanethiol
CH3 18-26%
I
CH3CHCH2CH2SH
 ALDEHYDE ACTION
3-mercapto-3-methyl-1-butanol
OH aldehyde

+ R-CHO

SH R
Alkylated
1,3-oxathiane

O S
 METAZENE
H O

C=C-C

H CH3 O-R

R=mixture from C 8H17 to C14H29

 GRILLOCIN
O C6H13
II I
C C-C2H3= CH

O O

C7H14 H Zn H C 7H14

O O

CH=C2H3 -C C
I II
C6H13 O
 CYCLODEXTRIN
A B

A B
a 0.57nm 1.37nm
ß 0.78nm 1.53nm
? 0.95mn 1.69nm
FRAGRANCE
& COLOR

Product is
formulated,
fragrance is chosen,
color is added,
time is short…
 CHROMOPHORES
Configurations which can
alter the energy of
delocalized systems

Benzene absorbs
around 200 nm
We see between 400-700 nm
VISIBLE STRUCTURES
Conjugated double bonds
-C=C-C=C-
AZO chromophore
-N=N-
N=N
BENZALDEHYDE + UV
-C=0
HC=0
UV

Free radical
 SYNESTHESIA

Relation of two
senses, such as
smell and color
 A ____
Name _______________________
B ____
C ____
D ____ 1 2 3
E ____
F ____
G ____
H ____ 4 5 6
I ____
J ____
K ____
L ____ 7 8 9
M ____
N ____
10 11
CINNAMIC
ALDEHYDE
RIFM/IFRA

For thirty years, the

fragrance industry
has had a continuous
program of safety
testing, and the
process has no end in
sight.
 PHYSIOLOGICAL
CONSIDERATIONS

• Skin irritation
• Phototoxicity
• Carcinogens
• Allergens
 NON-SKIN
CONTACT
• Solid air fresheners
• Plug-in air
fresheners
• Insecticides
• Toilet blocks
• Incense sticks
• Candles
• Plastic articles
SKIN CONTACT

• Aerosols
• Detergents
• Potpourri
• Carpet powders
• Household cleaning products
• Liquid refills for air fresheners
 Hydroxycitronellal
(Laurine, Hydronal, Phixia, Laurinal)
Last Amendment April 28, 2000
First Issued March 01, 1987
CAS # Recommendation Skin Contact Non-Skin Contact
107-75-5 Restricted 1% 10%
Hydroxycitronellal should not be used such that the level in consumer products
exceeds 1%. This is equivalent to 5% in a fragrance compound used at 20% in
the consumer product.
This recommendation is based on a no-effect level of 10% in diethyl phthalate
and on a no-effect level of 2.5% in ethanol/diethyl phthalate in standard Human
Repeated Insult Patch Tests (R.A. Ford and A.M. Api, Fd. Chem. Toxic. Vol. 26,
p. 921-926, 1988). The RIFM Expert Panel reviewed these data in
September 1999 and concluded that no further actions were required.
 CHEMICAL GROUPINGS
• A means to defend structurally related materials,
without having
to test every material in the group
– ~ 2,000 chemically defined
fragrance ingredients
– 22 Groups
(e.g. Acids, Acetals, Alcohols)
– > 60 Subgroups
(e.g. Straight chain saturated, straight chain
unsaturated etc.)
 RESPIRATORY SAFETY
• Selected fragrance ingredients
– Benzyl acetate
– Eugenol
– α-Hexyl cinnamic aldehyde (HCA)
– HHCB
– Hydroxycitronellal
– β-ionone
– d-limonene
– Linalool
– Methyl dihydrojasmonate
CHANDLER BURR

2002
www.stephen-herman.com
 Questions
or
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