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 25%
25% 50%
TOP
MIDDLE BOTTOM
Jean Carles: Evaluate volatility Construct accords Build from bottom up
CARLES BASE ACCORD Oakmoss Ambergris
9 8 7 6 5 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 1 6 4 1
Absolute Rose Absolute Civit 10% Oakmoss Ambergris 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 2 3 4 6 8
Name Monoterpene Sesquiterpene Diterpene Triterpene Tetraterpene
Formula C10H16 C15H24 C20H32 C30H48 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 H
O
S
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
Coumarin
O
NITROMUSKS C((CH)3)3
C((CH)3)3 NO2
NO2 CH3
CH3 NO2
Musk Xylene
NO2
NO2 NO2
CH3
CH3 C=O I CH3
Musk Ketone
POLYCYCLIC MUSKS
O
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 I OH CH3 I CH3CCH2CHCH3 I I OH OH
Butylene Glycol
Hexylene Glycol
SCHIFF BASE #1 Aldehyde + Amine H 2N
COOCH3
CHO + OH
HydroxyCitronellal
Methyl Anthranilate
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
Benzaldehyde
COOH
Benzoic Acid
POLYMERIZATION Aldehydes can Solidify
CH2CHO 2
Phenylacetaldehyde
OH I CH2CH-CHCHO
HEMIACETALS Aldehyde/Ketone + Alcohol
O II I C +- C- OH Loose, reversible aging hydroalcoholics
OH I C O C
ESTER HYDROLYSIS O OH
O -OH
Benzyl Acetate
Benzyl Alcohol
LACTONE HYDROLYSIS O -OH O
O
Epsilon Hexalactone
HO
6-Hydroxy Hexanoic Acid
OH
FRAGRANCE APPLICATIONSPERSONAL CARE
CHEMICAL EXAMPLES 1 PEA .
CH2CH2OH β-Pinene
CHEMICAL EXAMPLES 2 Hydroxycitronellal OH CH3 I
I
CH3CCH2CH2CH2CHCH2CH I II CH3 O
CH3 HOCH2CH2CH CH3 Amyl Alcohol
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 ImportantAliphatic 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
H3C
O
CH O
CONSEQUENCE
Fragrance will partition in phases of finished product
FUNCTIONAL FRAGRANCE • Economics • Stability • Translation
TEA-STEARATE EMULSION Air CH2CH2OH
PEA O
TEA-Stearate O
Hydroxycitronellal Pinene
Stearyl alcohol Amyl alcohol
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 Sodium Laureth Sulfate (A) Cocamidopropyl Betaine (B)
67.0 18.0 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
0
1
2
3
FRAGRANCE APPLICATIONSHOUSEHOLD PRODUCTS
Wt Loss
EVAPORATION CURVE
Days Typical Fragrance Evaporation Curve
Weight
FREE EVAPORATION
1
2 Time
3
4
Weight
LINEAR FRAGRANCE 4 3 2 1 Time
BLEACH Bleach unstable, affected by fragrance, solubilizer, oxygen, temperaturemust test chlorine and fragrance.
% NaOCl
DECOMPOSITION AT 100°F 5.6 5.4 5.2 5.0 4.8 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
Days
50 60
70
80
90 100 110 120 130 140 150
DOWFAX STRUCTURE SO3-X+
SO3-X+ O R
TITRATION 0.1 N Sodium Thiosulfate
Titrate until clear Stirring Bar Magnetic Stirrer
Bleach Test Mixture
MASKING/MALODOR Foul odors from bacterial decomposition or unpleasant molecules
FAMOUS MALODORS putrescine cadaverine spermidine
spermine
SKUNK ODOR H
CH2SH C=C
CH3
H
E-2-buten-1-thiol 38-44%
3-methyl-1-butanethiol 18-26%
CH3 I CH3CHCH2CH2SH
ALDEHYDE ACTION 3-mercapto-3-methyl-1-butanol
OH
aldehyde
R-CHO
+ R
SH
Alkylated 1,3-oxathiane
O
S
METAZENE
H
O C=C-C
H
CH3
R=mixture from C 8H17 to C14H29
O-R
GRILLOCIN O II C
C6H13 I C-C2H3= CH O
C7H14
O
H Zn H O
CH=C2H3 -C I C6H13
C 7H14
O C II O
CYCLODEXTRIN A B a ß ?
A 0.57nm 0.78nm 0.95mn
B 1.37nm 1.53nm 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=CAZO chromophore
-N=NN=N
BENZALDEHYDE + UV -C=0
HC=0
UV
Free radical
SYNESTHESIA
Relation of two senses, such as smell and color
Name _______________________
A ____ B ____ C ____ D ____ E ____ F ____ G ____ H ____ I ____ J ____ K ____ L ____ M ____ N ____
1
2
3
4
5
7
8
9
10
11
6
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
2002
CHANDLER BURR
www.stephen-herman.com
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