Perfumeryas a
Science
Steve Herman
FRAGRANCECREATION
VOLATILITY
For a moleculeTo have odor,MW<300 forappreciablevapor pressureat RT
BASIC COMPOSITION
FRAGRANCE TRIANGLE
TOP
MIDDLE
BOTTOM
25%
25%
50%
Jean Carles:Evaluate volatilityConstruct accords
Build from bottom up
CARLES BASE ACCORD
Oakmoss 9 8 7 6 5Ambergris 1 2 3 4 5
Selects 6:4, needed musk for chypre character:6 Oakmoss4 Ambergris1 Musk Ketone
ADD MIDDLE
Adds floral andanimal notes:
3 Absolute Rose1 Absolute Civit 10% 6 Oakmoss4 Ambergris1 Musk Ketone
TOP ADDED
Pleasant, highly volatile notes for sparkle:4 Sweet Orange Oil1 Bergamot3 Absolute Rose1 Absolute Civit 10% 6 Oakmoss4 Ambergris1 Musk Ketone
FRAGRANCECHEMICALS
CHEMICAL TYPES
• Alcohols• Aldehydes & Ketones• Aliphatic & Aromatic Esters• Nitriles• Ethers• Lactones• Heterocyclics• Terpenes
ALCOHOLS
R-OH Aliphatic
Aromatic
OH
ALDEHYDES & KETONES
HC=O
RAldehyde
R’C=O
R Ketone
TERPENES #1
Isoprene UnitsJoined Head To Tail
(C5H8)n C I
C=C-C=C
TERPENES #2
n Name Formula2 Monoterpene C10H163 Sesquiterpene C15H244 Diterpene C20H326 Triterpene C30H488 Tetraterpene C40H64
ACYCLIC TERPENES
β-Myrcene
MONOCYCLIC TERPENES
Limonene
BICYCLIC TERPENES
Pinene
SESQUITERPENE
γ-Bisabolene
NITRILES
R-C=N
C=N
Aliphatic
Aromatic
BASIC HETEROCYCLIC STRUCTURES
N
NH
O S
S+
O+
HETEROCYCLICS
NH
Indole
LACTONEA Cyclic Ester
γ or δ Hydroxy Acid forms 5 or 6 member ring by intramolecular esterfication
RCHCH2CH2COO-Na+
IOH
LACTONES
O O
Coumarin
NITROMUSKS
NO2
C((CH)3)3
NO2 NO2
CH3CH3
C=OI
CH3
Musk Xylene Musk Ketone
NO2
NO2
NO2
CH3CH3
C((CH)3)3
POLYCYCLIC MUSKS
Galaxalide
O
Propylene Glycol (PG)
FRAGRANCE DILUENTS 1CH3CHCH2-O-CH2CHCH3
I IOH 0H
Dipropylene Glycol (DPG)
CH3CHCH2OHI
OH
Hexylene Glycol
HOCH2CH2CHCH3I
OH
Butylene Glycol
CH3I
CH3CCH2CHCH3I IOH OH
FRAGRANCE DILUENTS 2
SCHIFF BASE #1
CHO +
OH
H2NCOOCH3
Hydroxy-Citronellal
MethylAnthranilate
Aldehyde + Amine
SCHIFF BASE #2
OH
CH=N
COOCH3
+ H2O
Aurantiol
CHEMICAL REACTIONS
HELPFUL REACTIONSPart of the naturalmaturing processHARMFUL REACTIONSOccur in isolated perfume oils or in reaction with base environment
STORAGE EFFECTS
• Elevated Temperatures• UV Radiation• Moisture• Oxidation
Accelerate changeor deterioration
AUTOOXIDATION
CHO COOH
Benzaldehyde BenzoicAcid
POLYMERIZATIONAldehydes can Solidify
Phenylacetaldehyde
2
CH2CHOOH I
CH2CH-CHCHO
HEMIACETALSAldehyde/Ketone + Alcohol
O OHII I IC +- C- OH C
OCLoose, reversible
aginghydroalcoholics
ESTER HYDROLYSIS
O
O
OH
-OH
Benzyl Acetate
BenzylAlcohol
LACTONE HYDROLYSIS
O O
O OH
HO
-OH
EpsilonHexalactone
6-HydroxyHexanoic Acid
FRAGRANCEAPPLICATIONS-
PERSONAL CARE
CHEMICAL EXAMPLES 1
PEA
. β-Pinene
CH2CH2OH
CHEMICAL EXAMPLES 2Hydroxycitronellal
Amyl Alcohol
CH3HOCH2CH2CH
CH3
OH CH3I I
CH3CCH2CH2CH2CHCH2CHI II
CH3 O
SOLUBILITY PARAMETER
Measure of all thecohesive forces in
a molecule
Refinement of“polar”
“nonpolar”division
CLOG P
CalculatedLOGarithm of theoctanol/waterPartitionCoefficient
Trinh et al 5,783,544, 1998
SMILES
SIMPLIFIED MOLECULARINPUT LINE ENTRY
SYSTEM
Allows entry of chemical structures into computer programs to predict
properties
EXAMPLE SMILESCase Important-Aliphatic Upper CaseAromatic Lower CaseHydrogen Not IncludedSINGLE BOND C-CDOUBLE BOND C=CTRIPLE BOND C#C
Rings- # at start and ende.g. c1ccccc1Br is Bromobenzene
CLOG P VANILLINSMILES: COc1cc(C=O)ccc1O
CH
O
HO
OH3C
CONSEQUENCE
Fragrance will partition in phases of finished product
FUNCTIONAL FRAGRANCE
• Economics• Stability• Translation
AirCH2CH2OH
Pinene
PEA
O
O
TEA-Stearate
Hydroxycitronellal
Stearyl alcohol
Amyl alcohol
TEA-STEARATE EMULSION
SURFACTANTSMore stable thanemulsions, butviscosity moreimportant, oftencolor problems
MICELLE EFFECTS
Water-MicelleInterface
Between Surfactant Molecules
Core ofMicelle
SURFACTANT VISCOSITY
Water 67.0Sodium Laureth Sulfate (A) 18.0Cocamidopropyl Betaine (B) 15.0
1. Unperfumed2. 2% Hydroxycitronellal3. 2% Phenylethyl Alcohol
A. Standapol ES-2 (COGNIS)B. Velvetex BK-35 (COGNIS)
VISCOSITY
0
200
400
600
800
1,000
1 2 3
FRAGRANCEAPPLICATIONS-HOUSEHOLD PRODUCTS
EVAPORATION CURVEW
t Los
s
DaysTypical Fragrance Evaporation Curve
FREE EVAPORATIONW
eigh
t
Time
1 2 3 4
LINEAR FRAGRANCEW
eigh
t
Time
1
2
3
4
BLEACH
Bleach unstable, affected byfragrance, solubilizer,oxygen, temperature-must test chlorine and fragrance.
Days0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
% N
aOC
l
5.65.45.25.04.84.64.44.24.03.83.63.43.23.02.8
DECOMPOSITION AT 100°F
DOWFAX STRUCTURE
O
SO3-X+ SO3
-X+
R
MagneticStirrer
StirringBar
BleachTestMixture
0.1 N Sodium Thiosulfate
Titrateuntilclear
TITRATION
MASKING/MALODOR
Foul odors frombacterial decompositionor unpleasant molecules
FAMOUS MALODORSputrescine
cadaverine
spermidine
spermine
SKUNK ODOR
H CH2SHC=C
CH3 HE-2-buten-1-thiol38-44%
3-methyl-1-butanethiol18-26%CH3
ICH3CHCH2CH2SH
ALDEHYDE ACTION
SH
OH
R-CHO+
R
O S
3-mercapto-3-methyl-1-butanol
aldehyde
Alkylated1,3-oxathiane
METAZENEH O
C=C-C
H CH3 O-R
R=mixture from C8H17 to C14H29
GRILLOCINO C6H13II IC C-C2H3= CH
O O
C7H14 H Zn H C7H14
O O
CH=C2H3 -C CI 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 isformulated,fragrance is chosen, color is added,time is short…
CHROMOPHORES
Configurations which can alter the energy ofdelocalized systems
Benzene absorbsaround 200 nmWe see between 400-700 nm
VISIBLE STRUCTURES
Conjugated double bonds
-C=C-C=C-AZO chromophore
-N=N-
N=N
BENZALDEHYDE + UV
HC=0-C=0
UV
Free radical
SYNESTHESIA
Relation of two senses, such as smell and color
1 2 3
4 5 6
7 8 9
10 11
A ____B ____C ____D ____E ____F ____G ____H ____I ____J ____K ____L ____M ____N ____N
ame
____
____
____
____
____
___
CINNAMIC ALDEHYDE
RIFM/IFRA
For thirty years, the fragrance industry has had a continuousprogram 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)
107-75-5 10%1%
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% inthe 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.
First IssuedLast Amendment April 28, 2000
March 01, 1987
RestrictedCAS # Recommendation Skin Contact Non-Skin Contact
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
CH
AN
DLE
R B
UR
R
2002
www.stephen-herman.com
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