Perfumery as Science (Steeve Herman)

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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