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Nattaya Lourith, Ph.D. 1
Basic fragrance chemistry I
2
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
Nattaya Lourith, Ph.D. 2
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O
OH
Lilial® Florol®Excital®
Orriniff®
Karanal®
Lyral®
Cedramber®
Boisambrebe®
Mayol®
Aldron®8
Functional groups with therapeutic actions
Anti-infectious, immunostimulantsAnti-infectious, immunostimulantsAnti-infectious, immunostimulantsEstrogen-like activityAnti-infections, calming, litholiticBalancing, calmingAntispasmodic, calmingBalancing, calmingCicatrizing (wound healing), mucolitic, litholitic, calmingExpectorant, antispasmodicAnti0infectious, immunostimulantsAnti-infectious, antispasmodicAnti-infectious, cortisone-like activityAntihistamines, anti-allergic
Acids Aromatics aldehydesC10 AlcoholsC15 & 20 AlcoholsAldehydesCoumarinsEstersLactonesKetones
OxidesPhenols Phenyl methyl ethersC10 TerpenesC15 Terpenes
Actions Functional 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, Quality Assurance
- Physical Chemistry – Emulsions, Light scattering, etc.- Psychological aspects of perception – other influences
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 analysis Volatiles from a living flower 12
Physical Chemistry
Nattaya Lourith, Ph.D. 3
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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 composed of the 6 elements in 99.9% w/w
And trace 17 elements
17 18
Pork fired rice
Cheese pizza
Nattaya Lourith, Ph.D. 4
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hemoglobin isbright 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
1Nucleus 0Neutron
1Nucleus+1Proton
MassLocation ChargeParticle
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
Nattaya Lourith, Ph.D. 5
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Chemical bonds
Two or more elements combine to form compound
- 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 compounds
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Fragrance compound name
DecNonOctHepHexPentButPropEthMethPrefix
10987654321C
Start with Prefix and end up with Suffix
-ate-ic-one-al-ol-yle-ene-aneSuffix
Functional group
Nattaya Lourith, Ph.D. 6
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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, l36
Hydrocarbon
Aliphaticalkane : single bond : CnH2n+2
alkene : double bond : CnH2n
alkyne : triple bond : CnH2n-2
cycloalkane : CnH2n
alicyclic : aliphatic cyclicAromatic
Nattaya Lourith, Ph.D. 7
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Alkane- 1C to 4C are colorless and odorless, flammable gases at ambient temp. & press.- 5C to 14C are colorless, flammable liquids, uninteresting odor- >15C are colorless, odorless, waxy solid
Hydrocarbon : Aliphatic
Lower alkanes are of no interest in perfumery, needed to remove as the extraction solvent from the extract
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Hydrocarbon : AliphaticAlkene
- unsaturated hydrocarbon- geometric isomers- molecular parent of terpene
buta-1,3-diene
methylbuta-1,3-diene
Alkane posses odor rather similar to the corresponding alkane but more odor strength due to double bond. Simple alkanes are not used as perfume ingredients.
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Terpene
Hydrocarbon : Aliphatic
Isoprene40
myrcene
Terpenemomoterpene : C10H16
sesquiterpene : C15H24(one and a half)
limonene α-pinene
Hydrocarbon : Aliphatic
farnesene
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Alkyne
- unpleasant, petroleum-like odor- no application in perfumery
But its derivative recently used as perfume ingredient give powerful green character
Hydrocarbon : Aliphatic
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Hydrocarbon : Aliphatic
cycloalkane CnH2n
alicyclic : aliphatic cyclic
Similar odor of those alkanehaving the same number of carbon
Nattaya Lourith, Ph.D. 8
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Hydrocarbon : Aromatic-Benzene is the prototype of aromatic compounds
1865 Friedrich August Kekulé
- Bezenoid compound posses sweet and pleasant odorDimethylbenzene or Xylene
1,2-dimethylbenzeneortho-dimethylbenzeneo-dimethylbenzene
1,3-dimethylbenzenemeta-dimethylbenzenem-dimethylbenzene
1,4-dimethylbenzenepara-dimethylbenzenep-dimethylbenzene 44
Alcohols & Phenols : R-OHEthers : R-O-RAldehydes : R-CHOAcetals : 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 & PhenolsSome alcohol of interest to perfumer
NACreamy mushroom3-octen-2-ol1.2 ppb (H2O)Powerful mushroom1-octen-3-ol1550 ppb (H2O)Green, grassy and leafyE-3-hexen-1-ol70 ppb (H2O)Herbaceous, green, grassyZ-3-hexen-1-ol400 ppb (H2O)Green, leafyE-2-hexanolNAFresh green, leafyZ-2-hexanol
Odor detection threshold
OrganolepticsAlcohol
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Pure phenol is colorless crystal with clean and antiseptic odor
Phenol was the first antiseptic ever usedPure phenol is very dangerous cause extremely
painful skin burn
OH
Alcohols & Phenols
O
OH
OHEugenol
Thymol
Glucoside form in oil of cloves, 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, very powerful
CH3(CH2)5CHOHeptanal4.5 ppb (H2O)Fruity green, very powerfulCH3(CH2)4CHOHexanal12.0 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, fruityCH3CH2CHOPropanal8.7 ppb (H2O)Choking, vinous, fruityCH3CHOAcetaldehyde
Odor detection threshold
OrganolepticsFormula Aldehydes
Important aldehyde in perfumery = C8-C13
Perfume industry tends to speak of aldehyde C12 rather than dodecanal
Nattaya Lourith, Ph.D. 9
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Acetals
RO
R
OH
RO
R
OR
OO
Hemi-acetal Acetal
- Acetal posses interesting and useful odor- Acetal is alkali stable
PADMA = phenyl-acetaldehyde dimethyl acetal
O
O
acetaldehyde di-cis-3-hexenyl acetal
Perfume, green relates to hyacinth and watercress
Sweet and Green 50
Ketones
Acetone (aketon German) rose to ketoneAcetone has a rather harsh, etheral and unpleasant odor
used as a simple and inexpensive nail varnish remover
Fruity, orange like, floralCH3CO(CH2)7CH3DecanoneFruity, floral, herbaceousCH3CO(CH2)6CH3Nonanone
Floral, green fruity, herbaceous
CH3CO(CH2)5CH3OctanoneSweet, fruity, spearmintCH3CO(CH2)4CH3HeptanoneEthereal, fruityCH3CO(CH2)3CH3Hexanone
Fruity, orange like, waxy, floralCH3CO(CH2)8CH3Undecanone
Ethereal, not unpleasantCH3CO(CH2)2CH3PentanoneEthereal, not unpleasantCH3COCH2CH3ButanoneHarsh, etherealCH3COCH3PropanoneOrganolepticsFormula Ketones
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Esters
1.0 ppb (H2O)Ethereal, fruity, butteryEtOOC(CH2)2CH3Ethyl butyrate1.5 ppb (H2O)Strong, fruity, appleEtOOC(CH2)3CH3Ethyl valerate1.0 ppb (H2O)Strong, fruity, wine, apple,
banana, pineappleEtOOC(CH2)4CH3Ethyl hexanoate
2.2 ppb (H2O)Strong, fruity, wine, cognacEtOOC(CH2)5CH3Ethyl heptanoate
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-brandy like
EtOAcEthyl acetate
Odor detection threshold
OrganolepticsFormula Esters
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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
Nattaya Lourith, Ph.D. 10
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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
Nattaya Lourith, Ph.D. 11
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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
Nattaya Lourith, Ph.D. 12
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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
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. 2nd ed.
Trowbridge: Micelle Press; 2001.3. Arctander S. Perfume and Flavor Chemicals (Aroma
Chemicals). V. 1. Illinois: Allured; 1994. 4. Gimelli SP. Aroma Science. New York: Micelle Press;
2001. 5. Nattaya L. Fragrance Chemistry in Aromatic Science
1701351 [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. From
virgin education to real education. Chem. Biodiv. 5: 1159-1169, 2008.
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Thank you for your attention