Basic Fragrance Chemistry

8/9/2019 Basic Fragrance Chemistry

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Nattaya Lourith, Ph.D. 1

Basic fragrancechemistry I

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Objectives:

• Basic element• Chemical functional group of aroma

compounds

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Contents:

• Introduction

• Functional group

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Flower and Chemistry

• Smell a Flower

– The Fragrance is Chemistry

• See a Flower

– The Colour is Chemistry

• Touch a Flower

– The Structure is Chemistry

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Carnation• Flower

• Eugenol

• Perfume & Cosmetics

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Vanilla• Seed

• Vanillin

• Perfume


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O

OH

Lilial®

Florol®Excital®

Orriniff®

Karanal®

Lyral®

Cedramber®

Boisambrebe®

Mayol®

Aldron® 8

Functional groups with therapeutic actions

Anti-infectious, immunostimulants

Anti-infectious, immunostimulantsAnti-infectious, immunostimulants

Estrogen-like activity

Anti-infections, calming, litholitic

Balancing, calming

Antispasmodic, calming

Balancing, calming

Cicatrizing (wound healing), mucolitic, litholitic,calming

Expectorant, antispasmodic

Anti0infectious, immunostimulants

Anti-infectious, antispasmodic

Anti-infectious, cortisone-like activity

Antihistamines, anti-allergic

Acids

Aromatics aldehydesC10 Alcohols

C15 & 20 Alcohols

Aldehydes

Coumarins

Esters

Lactones

Ketones

Oxides

Phenols

Phenyl methyl ethers

C10 Terpenes

C15 Terpenes

ActionsFunctional group

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Chemistry/Biology/Physiology/Psychology- Organic Chemistry – Synthetic, Molecular structure,

Biochemistry, Molecular Biology, Genomics,Anatomy, Neuroscience, Bioinformatics

- Analytical Chemistry – GC-MS analysis, QualityAssurance

- Physical Chemistry – Emulsions, Light scattering, etc.- Psychological aspects of perception – otherinfluences

Computer Science – for all of the above +

OLFACTION & GUSTATIONMultidisciplinary Fields

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Organic Chemistry

Organic synthesis

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Analytical Chemistry

GC-MS analysisVolatiles from a living flower 12

Physical Chemistry


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Artificial nose

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15 16

Elements for Life

• C : Carbon

• H : Hydrogen

• N : Nitrogen

• O : Oxygen

• P : Phosphorus• S : Sulfur

Living organisms composedof the 6 elements in 99.9%w/w

And trace 17 elements

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Porkfiredrice

Cheesepizza


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hemoglobin is

bright redcontainingIron (Fe)

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Organic and Inorganic substances

• Organic

– C, H, N, O, P, S

• Inorganic

– Metal

–Salt

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Weight & Number

0Shell-1Electron

1Nucleus0Neutron

1Nucleus+1ProtonMassLocationChargeParticle

Atomic weight = Proton + Neutron

Atomic number = Proton

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Structure

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Chemical bonds : Octet rule

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Chemical bonds : Electronegativity


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Chemical bonds

Two or more elementscombine to formcompound

- Covalent bonds

- Ionic bonds

- Hydrogen bonds

26Covalent bonds

27Ionic bonds 28

Hydrogen bonds

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Fragrance and Chemical functional group

- Hydrocarbon

- Oxygen compounds

- Nitrogen compounds

- Sulfur compounds

- Heterocyclic compounds

- Halogen compounds30

Fragrance compound name

DecNonOctHepHexPentButPropEthMethPrefix

10987654321C

Start with Prefix and end up with Suffix

-ate-ic-one-al-ol-yle-ene-aneSuffix

Functional group


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Structure writing

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Isomers

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Isomers

Cis or Z Trans or E

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Isomers

R, S or (+), (-) or d, l 36

HydrocarbonAliphatic

alkane : single bond : CnH2n+2alkene : double bond : CnH2nalkyne : triple bond : CnH2n-2

cycloalkane : CnH2nalicyclic : aliphatic cyclic

Aromatic


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Alkane- 1C to 4C are colorless and odorless,flammable gases at ambient temp. & press.

- 5C to 14C are colorless, flammableliquids, uninteresting odor

- >15C are colorless, odorless, waxy solid

Hydrocarbon : Aliphatic

Lower alkanes are of no interest in perfumery, neededto remove as the extraction solvent from the extract

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Alkene- unsaturatedhydrocarbon

- geometric isomers

- molecular parent ofterpene

buta-1,3-diene

methylbuta-1,3-diene

Alkane posses odor rather similar to the correspondingalkane but more odor strength due to double bond.Simple alkanes are not used as perfume ingredients.

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Terpene


Isoprene40

myrcene

Terpenemomoterpene : C10H16

sesquiterpene : C15H24(one and a half)

limonene α-pinene


farnesene

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Alkyne

- unpleasant, petroleum-like odor

- no application in perfumery

But its derivative recently used asperfume ingredient give powerful greencharacter


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Hydrocarbon : Aliphaticcycloalkane CnH2nalicyclic : aliphatic cyclic

Similar odor of those alkanehaving the same number ofcarbon


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Hydrocarbon : Aromatic

-Benzene is the prototype of aromatic compounds

1865 Friedrich August Kekulé

- Bezenoid compound posses sweet and pleasant odor

Dimethylbenzene or Xylene

1,2-dimethylbenzeneortho -dimethylbenzeneo -dimethylbenzene

1,3-dimethylbenzenemeta -dimethylbenzenem -dimethylbenzene

1,4-dimethylbenzene para -dimethylbenzene p -dimethylbenzene 44

Alcohols & Phenols : R-OHEthers : R-O-RAldehydes : R-CHO

Acetals : R-C(OR)2Ketones : R-CORCarboxylic acids : R-COOHEsters : R-COORLactones : O

O

Oxygen compounds

O O

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Substitute group : R

C

H

H

C

H

H

C

H

H

C

H

H

H HC

H

H

C

H

H

C

H

H

C

H

H

C

H

H

H C

H

H

PentylPentane

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Alcohols & Phenols

Some alcohol of interest to perfumer

NACreamy mushroom3-octen-2-ol

1.2 ppb (H2O)Powerful mushroom1-octen-3-ol1550 ppb (H2O)Green, grassy and leafyE -3-hexen-1-ol

70 ppb (H2O)Herbaceous, green, grassyZ -3-hexen-1-ol

400 ppb (H2O)Green, leafyE -2-hexanol

NAFresh green, leafyZ -2-hexanol

Odor detectionthreshold

OrganolepticsAlcohol

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Pure phenol is colorless crystal with clean andantiseptic odor

Phenol was the first antiseptic ever used

Pure phenol is very dangerous cause extremelypainful skin burn

OHAlcohols & Phenols

O

OH

OHEugenol

Thymol

Glucoside form in oil ofcloves, pale yellow liquid,strong odor. Antibacterial,antifungal

Perfumes, Soaps, Cosmetic

Thyme and ajowanoil, white solid,thyme odor

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AldehydesAldehyde = alcohol dehydrogenatum Latin

= dehydrogenated alcohol English

3.0 ppb (H2O)Vinous fruity, coarse, verypowerful

CH3(CH2)5CHOHeptanal

4.5 ppb (H2O)Fruity green, very powerfulCH3(CH2)4CHOHexanal

12.0 ppb (H2O)Choking, pungent, fruity, oilyCH3(CH2)3CHOPentanal

0.7 ppb (H2O)Orange peel, fatty, very powerfulCH3(CH2)6CHOOctanal

9.0 ppb (H2O)Choking, pungent, fruityCH3(CH2)2CHOButanal

9.5 ppb (H2O)Choking, suffocating, fruityCH3CH2CHOPropanal

8.7 ppb (H2O)Choking, vinous, fruityCH3CHOAcetaldehyde


OrganolepticsFormulaAldehydes

Important aldehyde in perfumery = C8-C13Perfume industry tends to speak of aldehyde C12 rather than dodecanal


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Acetals

RO

R

O

H

RO

R

O

R

OO

Hemi-acetal Acetal

- Acetal posses interestingand useful odor- Acetal is alkali stable

PADMA = phenyl-acetaldehyde dimethyl acetal

O

O

acetaldehyde di-cis -3-hexenyl acetal

Perfume, green relates tohyacinth and watercress

Sweet andGreen 50

Ketones

Acetone (aketon German ) rose to ketone

Acetone has a rather harsh, etheral and unpleasant odorused as a simple and inexpensive nail varnish remover

Fruity, orange like, floralCH3CO(CH2)7CH3Decanone

Fruity, floral, herbaceousCH3CO(CH2)6CH3Nonanone

Floral, green fruity,herbaceous

CH3CO(CH2)5CH3Octanone

Sweet, fruity, spearmintCH3CO(CH2)4CH3Heptanone

Ethereal, fruityCH3CO(CH2)3CH3Hexanone

Fruity, orange like, waxy, floralCH3CO(CH2)8CH3Undecanone

Ethereal, not unpleasantCH3CO(CH2)2CH3Pentanone

Ethereal, not unpleasantCH3COCH2CH3Butanone

Harsh, etherealCH3COCH3Propanone

OrganolepticsFormulaKetones

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Esters

1.0 ppb (H2O)Ethereal, fruity, butteryEtOOC(CH2)2CH3Ethyl butyrate

1.5 ppb (H2O)Strong, fruity, appleEtOOC(CH2)3CH3Ethyl valerate

1.0 ppb (H2

O)Strong, fruity, wine, apple,banana, pineapple

EtOOC(CH2

)4

CH3

Ethyl hexanoate

2.2 ppb (H2O)Strong, fruity, wine, cognacEtOOC(CH2)5CH3Ethylheptanoate

15.0 ppb (H2O)Fruity, wine, sweet, cognac-apricot

EtOOC(CH2)6CH3Ethyl octanoate

850.0 ppb(H2O)

Fatty, oily, cognac, nutEtOOC(CH2)7CH3Ethyl nonanoate

10.0 ppb (H2O)Strong, ethereal, fruity, rumEtOOCEtEthyl propionate

5000.0 ppb(H2O)

Ethereal, sharp, wine-brandylike

EtOAcEthyl acetate


OrganolepticsFormulaEsters

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Cinnamon

• Bark

• Cinnamaldehyde

• Perfume

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Cinnamon

• Leaf• Eugenol• Vanillin raw material

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Citronella• Leaf

• Citronellol

• Soap & Cosmetics


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Clove

• Bud

• Eugenol

• Perfume

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Cumin

• Seed• Cuminaldehyde

• Perfume

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Eucalyptus

• Leaf

• Cineole• Fixative

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Fennel

• Seed

• Anethole

• Oral care

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Geranium• Stem & Leaf

• Geraniol

• Perfume

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Hyacinth• Flower

• Benzyl acetate

• Fragrant


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Jasmine

• Flower• Benzyl acetate• Floral perfume

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Lavender

• Flower• Linalool• Perfume & Soap

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Lemongrass• Leaf• Citral• Soap & Detergent

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Nutmeg

• Seed coat• i -Camphene• Oral care

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Orange • Fruit peel• d -Limonene• Perfume & Lipstick

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Orange• Flower

• Linalool

• Perfume & Cosmetics


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Patchouli

• Leaf• (-)-Patchoulol

• Perfume

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Pennyroyal

• Stem• d -Pulegone

• Soap

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Peppermint• Leaf

• i -Menthol

• Oral care

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Rose

• Flower

• i -Citronellol

• Perfume

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Sandalwood• Wood & Root• Santalol• Fixative

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Spearmint• Leaf

• i -Carvone

• Oral care


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Nattaya Lourith Ph D 13

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Star anise

• Fruit• Anethole• Perfume

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Thyme

• Leaf & Flower• Thymol• Soap

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Wintergreen

• Leaf• Methyl salicylate• Oral care

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Ylang ylang• Flower

• Benzyl acetate

• Perfume

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References1. Butler H, editor. Poucher’s Perfume, Cosmetics and

Soaps. 10th ed. Dordrecht: Kluwer; 2000.

2. Curtis T, William DG. Introduction to Perfumery. 2 nd ed.Trowbridge: Micelle Press; 2001.

3. Arctander S. Perfume and Flavor Chemicals (AromaChemicals). V. 1. Illinois: Allured; 1994.

4. Gimelli SP. Aroma Science. New York: Micelle Press;2001.

5. Nattaya L. Fragrance Chemistry in Aromatic Science1701351 [Lecture handout]. Chiangrai: MFU.

6. Ellena C. Perfume formulation: words and chats. Chem.Biodiv. 5: 1147-1153, 2008.

7. Laudamiel C., Hornetz C., Mookherjee BD., Patel S. Fromvirgin education to real education. Chem. Biodiv. 5: 1159-1169, 2008.

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Thank you for your attention

Basic Fragrance Chemistry

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