Post on 22-Apr-2018
Nattaya Lourith, Ph.D. 1
Fragrance Chemistry
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Objectives:
• Relation of fragrance chemistry and odor
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Contents:
• Functional group and odor relation• Molecular weight and odor relation• Isomer and odor relation
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Bergamot oil
1. α-pinene
2. sabinene
3. β-pinene
4. β-myrcene
5. ρ-cymene
6. d-limonene
7. γ-terpinene
8. linalool
9. linalyl acetate5%, 1 μl, 1:100 split, He, 36 cm/s, 46.7 kPa, 40 °C-300 °C, 5 °C/min, Rtx5SilMs, Shimadsu GCMS-QP2010
Chemical combinations of floral fragrances
55---21Eugenol
2-25525Terpineol
460-543Ionone 31040545Benzyl acetate
1145524Amyl cinnamaldehyde
54220482Geraniol
55645-30Hydroxycitronellal
25205153530Phenyl ethyl alcohol
CarnationViolet Jasmine MuguetRose Lilac Types
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Fragrances in productsNumber of listed fragrance in each products
Nattaya Lourith, Ph.D. 2
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Frequency of fragrance in products
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Fragrances in deodorants
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Export value of Thai cosmetics
2009;Jan-Aug ‡ 2010;Jan-Aug
• 38.68% increase• 1,359.21 MUSD
0.571.6729.2015.9028.4623.540.66
Fragrance Oral careSoap Body odor care
Skin care & make up
Raw mat.
Hair
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Fragrance and Chemical functional group
- Hydrocarbon- Oxygen compounds- Nitrogen compounds- Sulfur compounds- Heterocyclic compounds- Halogen compounds
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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 12
Ethers
Fatty, wet sheepCH3(CH2)6O(CH2)8CH3Heptyl nonyl ether
Oily, earthy greenCH3(CH2)6O(CH2)7CH3Heptyl octyl ether
Wet sheep, metallicCH3(CH2)6O(CH2)6CH3Di-heptyl ether
Green CH3(CH2)6O(CH2)5CH3Heptyl hexyl ether
Sharp, green, leafyCH3(CH2)6OCH3Heptyl methyl ether
Sharp, oily greenCH3(CH2)6OCH2CH3Heptyl ethyl ether
Fruity CH3(CH2)6O(CH2)2CH3Heptyl propyl ether
Buttery, green, metallic
CH3(CH2)6OCH(CH3)2Heptyl isopropyl ether
Oily green, freshCH3(CH2)6O(CH2)4CH3Heptyl pentyl ether
Herbal, oily freshCH3(CH2)6O(CH2)9CH3Heptyl decyl ether
OrganolepticsFormula Ethers
Nattaya Lourith, Ph.D. 3
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Carboxylic acids
Pelagronic acidC8H17COOH9
Margaric acidC16H33COOH17
Arachidic acidC19H39COOH20Stearic acidC17H35COOH18
Myristic acidC13H27COOH14Palmitic acidC15H31COOH16
Behenic acidC21H43COOH22
Lauric acidC11H23COOH12Capric acidC9H19COOH10
Caprylic acidC7H15COOH8Valeric acidC4H9COOH5Traditional and/or INCI nameFormulaCarbon
Phenyl acetic acid
Posses a persistent odor of Honey and Civet
OH
O
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LactonesCertain macrocyclic lactones
posses beautiful, delicate and musky odor
Very important as fine fragrance aroma chemicals
γ-lactones so called butanolide
OO
O O
γ-lactone
δ-lactone
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Lactones
7 ppb (H2O)Fatty, fruity, peach4-octylbutanolide
950 ppb (H2O)Strong fatty, peach-apricot
4-heptylbutanolide
11 ppb (H2O)Coconut-peach4-hexylbutanolide
65 ppb (H2O)Strong, fatty, coconut
4-pentylbutanolide
7 ppb (H2O)Sweet coumarin, coconut-like
4-butylbutanolide
400 ppb (H2O)Coconut, hay-like, coumarin
4-propylbutanolide
1 600 ppb (H2O)
Coumarin, sweet, creamy
4-ethylbutanolide
10 000 ppb (Beer)
Sweet, hay-like, coumarin
4-methylbutanolide
Odor detection threshold
OrganolepticsFormula Lactones
(CH2)2CH3O O
(CH2)3CH3O O
(CH2)4CH3O O
(CH2)5CH3O O
(CH2)6CH3O O
(CH2)7CH3O O
O O
CH2CH3O O
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Nitrogen compounds
Amines : R-NH2Enamines & Imines : R-N=CHR’ & R-C=NHR’Nitriles :Lactams :
R C N
ONH
NH
Oγ-lactam δ-lactam
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Nitrogen compounds
NH2H2N
Simple amines having 1 to 3 alkyl groups smell fishy, otherwise animalic odor
1,4-diaminobutane or putrescine
NH2H2N
foul odor of putrefying flesh and contribute to the odor ofbad breath and bacterial vaginosis
1,5-diaminopentane or cadaverine
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Sulfur compounds- Thiols (Mercaptans) : R-SH
- Thioaldehydes : R-CSH
- Thioketones : R-CSR’
- Thioacids : R-COSH or R-CSSH
- Sulfides : R-SnH
- Isothiocyanates : R-NCS
Nattaya Lourith, Ph.D. 4
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Sulfur compounds
Powerful pineappleThioester/Thioketone
Methylsulfanyl-acetic acid methyl ester
Strong onion, meaty, sweet
Thioaldehyde3-Methylsulfanyl-propionaldehyde
Garlic, cabbageSulfide4-Methylsulfanyl-butan-1-ol
Sulfury, coffee, roasted
ThioacidThioacetic acid S-ethyl ester
Strong garlic, cabbage
Thiol3-Mercapto-butan-2-ol
Garlic, sulfuryThiolButanethiol
Onion, garlicThiolProp-2-ene-1-thiolOrganolepticsFormulaClassName
SH
SHHO
SHS OH
S H
O
S
O
S O
O
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Heterocyclic compounds in fragrance
- Furan
- Thiophene
- Pyrrole
O
- Thiazole
- Oxazole
- Pyrazole
- Pyrazine
- Pyridine
- Pyran
S
NH
S
N
O
N
NHN
N
N
N
O
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The most heterocyclic compounds contribute in fragrance are
Major heterocyclic compounds in fragrance
- Pyrazine- Thiazole- Furan
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Pyrazine
400 ppb (H2O)
Nutty, baked potato, roasted peanut, cocoa
C7H10N22,3,5-Trimethylpyrazine
200 ppb (H2O)
Chocolate, roasted nut, fired potato
C6H8N22,6-Dimethylpyrazine
800 ppb (H2O)
Chocolate, roasted nut, Chocolate, roasted nut, earthy
C6H8N22,5-Dimethylpyrazine
2 500 ppb (H2O)
Green, nutty, potato, cocoa, coffee, caramel
C6H8N22,3-Dimethylpyrazine
6 000 ppb (H2O)
Musty, nutty, buttery, peanut
C6H8N22-Ethylpyrazine
Detection threshold
OrganolepticsStructure Molecular formula
Pyrazine
N
N
N
N
N
N
N
N
N
N
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Thiazole
Cocoa, nutty, coffee2,4,5-trimethylthiazole
Cabbage, sulfury, vegetable2-Methyl-5-methoxythiazole
Hazelnut, nutty, cocoa4-Methyl-5-vinylthiazole
Green, herbal, nutty2-Propionylthiazole
Pyridine-like, nuttyThiazoleOganolepticsFormulaThiazole
S
N
S
NO
S
N
O
S
N
S
N
Thiazoles are useful in perfumes and cosmetics due to their occurrence in nature and interesting organoleptic properties.
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Furan
Furans are important in fragrance in which a natural character is desired.
Rose furan was first isolated from rose oil.
Rose oxide and rose furan occur in geranium oil.
Linalool is very important for reconstitution of lavender oil.
Fruity, banana-like in dilution
Furfurylacetate
Coffee, nutty, roasted
Furfurylthioacetate
Caramel, bread, burnt
Furfural
Coffee, roasted, sulfuric
Furfurylmercaptan
Coconut, burnt potato
Furfuryl alcohol
OganolepticsFormulaFuran
OOH
OSH
OO
O
S
O
O
OO
Nattaya Lourith, Ph.D. 5
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Functional group and odor property
Ethereal, not unpleasant
2-ButanoneCH3CH2COCH3
Choking, pungent, fruity
1-ButanalCH3(CH2)2CHO
Choking, hash, vinous
1-ButanolCH3(CH2)3OH
OdorStructural formula
IUPAC names
Molecular formula
HO
CHO
O
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Waxy, floralHexadecanolEarthy, waxy, fattyDodecanolCitrus, green, sweetUndecanol
Floral, fruity, waxyDecanolRose, citrusNonanol
OrganolepticAlcohol
Alcohol and organoleptic
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Aldehyde and organoleptic
Rose, orange, fattyUndecanalFloral, waxy, herbaceousDodecanal
Floral, citrus, waxyDecanal Floral, orange, roseNonanalFatty, citrus, honeyOctanalFatty, woody, oilyHeptanal
OrganolepticAldehyde
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Ketones and organoleptic
Warm, spicy, herbaceous
TridecanoneFloral, fruityNonanoneFloral, fruity, greenOctanoneSpicy, cinnamonHeptanoneEthereal, fruity PentanoneEthereal Butanone Ethereal, fruityPropanoneOrganoleptic2-ones
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Carboxylic acids and organoleptic
Rancid, fatty, oilyOctanoicRancid, fatty, sweatyHeptanoicCheese, rancid, fattyHexanoicPutrid, fecalPentanoicCheese, rancidButanoicPungent, rancidPropanoicVinegary Acetic OrganolepticAcid
30Bell pepper, peasCH3i-C4H9
Potato chipsC2H5CH3CONuttyCH3CH3CONutty, popcornHCH3CONutty, cocoaCH3CH3ONutty, cocoaHCH3O
Odor R’R
Pyrazine derivatives and organoleptics
N
N R
R'
Nattaya Lourith, Ph.D. 6
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Nutty, cocoaCH3CH3CH3
Nutty, greenHCH3H
Coffee COCH3CH3HNutty, cerealCH3OHHNutty, green, leafy HC2H5CH3
Nutty CH3C2H5CH3
Odor R”R’R
Thiazoles derivatives and organoleptics
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Fruity COOCH3
Stinging COOHSweet, bread-likeCHO
Coconut, burnt potato
OHBalsamic CH3CO
Caramel FurfurylBeany, grassy, greenC5H11
Sweet, coffee-likeC2H5
Ethereal CH3
OrganolepticR
•H2CO
O R
Furans derivatives and organoleptics
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Molecular weight and odor character
Fatty-floral-rose, waxy
1-NonanalCH3(CH2)7CHO
Fatty-fruity, sweet, citrus-orange
1-OctanalCH3(CH2)6CHO
Fatty, sweet, fruity, nutty
1-HeptanalCH3(CH2)5CHO
Fatty-green, grassy unripe fruit odor
1-HexanalCH3(CH2)4CHO
Strong acid, pungent1-PentanalCH3(CH2)3CHO
Green CH3CHO-like, green coffee
1-PropanalCH3CH2CHO
Pungent, nutty alcoholic
AcetaldehydeCH3CHO
Choking, lachrymatory
HCHOFormaldehydeHCHO
OdorSkeleton formulaIUPAC namesMolecular formula
O
O
O
O
O
O
O34
Ethyl esters and organoleptic
Wine, fruityHexanoateStrong, applei-ValerateApple ValerateCitrus i-ButyrateSweet, fruityButyrate Pineapple Acetate Sweet, rumFormate
organolepticEthyl esters
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Green, teaButyrateWoody, fruityAcetate Fruity, fattyFormateOrganolepticHeptyl esters
Heptyl esters and organoleptic
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Geraniol esters and organoleptic
GeraniumTiglate
Rose, geranium
CaproateRose i-ButyrateRose, applen-ButyrateRose Propionate
Rose, lavender
Acetate Rose leafFormateOrganolepticEster
Nattaya Lourith, Ph.D. 7
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Linalool esters and organoleptic
Fruity, applei-ValerateLavender i-Butyrate
Bergamot, fruity
n-Butyrate
Bergamot, peach
PropionateFloral, fruityAcetate Citrus, herbalFormate
OrganolepticEster
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Citronellol esters and organoleptic
Fruity, roseTiglateRose Caproate
Honey, herbaceous
ValerateFruity, rosei-ButyrateFruity, rosen-ButyrateFruity, rosePropionate Citrus, roseAcetate Peach, plum, roseFormate
OrganolepticEster
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Menthol esters and organoleptic
Citrus Lactate Fruity, woodyi-Valerate
Berry, minty, woody
Acetate OrganolepticEster
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Benzyl alcohol esters and organoleptic
FixativeBalsamic CinnamateFixative None Salicylate
Fixative Floral Phenyl acetate
Fixative Faint, balsamicBenzoate
Modifier Fruity, floral, herbaceous
i-ValeratePerfumes Fruity, jasminei-Butyrate
Solvent, fixative
Floral, fruity, plumn-ButyratePerfumes Floral, fruity, berryPropionate PerfumesFloral, fruityAcetate
Uses OrganolepticEster
OH
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Benzoic acid esters and organoleptic
Fixative Dried rose petals
Citronelly
Perfumes Heavy floralLinalyl
Modifier Soft, sweetGeranylFixative Soft OctylFixative Ambergris i-AmylFixative Balsamic Butyl Soaps Mild floralEthyl SoapsHarsh floralMethyl
Uses OrganolepticEster COOH
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Salicylic acid esters and organoleptic
Perfumes Balsamic PhenylethylCosmetics, soapsOrchid, hayi-Amyl Perfumes Wintergreen Butyl Modifier Fruity Allyl
Soaps, dental products
Wintergreen Ethyl
Soaps, dental products
Wintergreen Methyl Uses OrganolepticEster
OHCOOH
Nattaya Lourith, Ph.D. 8
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Cinnamic acid esters and organoleptic
FloralLily, jasmineLinalylFloral Fragrant TerpenylHeavy typeSweet, balsamicCinnamylFixative Balsamic PhenylpropylFixative Balsamic PhenylethylOriental, floralHeavy sweetBenzyl Bouquets, soapsAmber i-AmylOriental Sweet amberi-ButylOriental, floralSweet amberEthyl
Oriental, floralHeavy, amber, fruity
Methyl Uses OrganolepticEster
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Positional isomer and odor relation
Herbaceous3-Heptanol
Earthly, oily2-Heptanol
Fragrant, woody
1-Heptanol
OdorStructural formulaIUPAC names
OH
OH
OH
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Organoleptic4-ones Fruity, pineappleHeptanone
Citrus, rose, irisUndecanoneFloral, citrus, greenDecanoneLeafy, herbaceousNonanoneSpicy, butteryOctanoneFruity, green, fatty HeptanoneGrape, wine-likeHexanoneOrganoleptic3-ones
Positional isomer and odor relation
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Mint(-)-Limonene
Citrus(+)-Limonene
Spearmint(-)-Carvone
Caraway(+)-Carvone
OdorStructural formula
IUPAC names
Optical isomer and odor relation
O
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Fruity, fattytrans-3-Hexen-1-olGreen, grassy
cis-3-Hexen-1-ol
Leafy green, fruitytrans-2-Hexen-1-ol
Greencis-2-Hexen-1-ol
OdorStructural formulaIUPAC names
Geometric isomer and odor relation
HO
HO
OH
HO
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Conformational isomer and odor relation
Woody
Woody
Fruity, woody, bitter
Grapefruit, bitter
6-Isopropyl-4-,4a-dimethyl-4-4a,5,6,7,8-hexahydro-3H-naptalen-2-one OR Nootkatone
OdorStructural formula
IUPAC names
O
O
O
O
Nattaya Lourith, Ph.D. 9
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Nootkatone
First isolated in 1962Isolation from grapefruit in 1964
In 1966, Coca-Cola introduced Fresca
OO
(+)-Nootkatonestrong grapefruit odor,
bitter in taste
(-)-Nootkatoneweak woody (vetiver note);no grapefruit character;
virtually no tasteThreshold: 60,000 ppb 800 ppb 50
Saturated-unsaturated compounds and odor relation
Peach6-Pentylpyran-2-one
Creamy, sweet6-Pentyl-tetrahydropyran-2-one
OdorStructural formula
IUPAC names
OC5H11 O
OC5H11 O
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Isomer and odor
35431825IsoESuper
Déclaration(Cartier)
Féminitédu Bois (Shiseido)
Trésor(Lancôme)
Fahrenheit (C. Dior)
%
Iso E Super®
500 ng/l
5 ng/l Georgywood®
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Orris, green, violet
Orriniff®4-(5-methylbicyclo[2.2.1]hept-5-en-2-yl)pyridine
IFF
Fresh & cleanLilial®3-(4-tert-butylphenyl)-2-methylpropanalGivaduan
OrganolepticsName Structure
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Cool water (Davidoff)
Hesperidic, floral, fresh
Dihydro-myrcenol
Mitsouko(Guerlain)
Fruity, peachγ-undecalactone
Eau Sauvage(C. Dior)
Floral, jasmine
Hedione®
Chanel N°5Aldehydic, fatty, orange
Laurylaldehyde
Perfume OrganolepticsName Structure
CO2Me
O54
2,6-dimethylhept-5-enal
Melonal®
3-(4-ethylphenyl)-2,2-dimethylpropanal
Floralozone®
3-(benzo[d][1,3]dioxol-5-yl)-2-methylpropanal
Tropional®
7-methyl-2H-benzo[b][1,4]dioxepin-3(4H)-one
Calone 1951®
Name Structure
Nattaya Lourith, Ph.D. 10
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Aquatic perfume combination
0.040.070.1---Floralozone
0.120.020.030.02--Melonal
4.84.31.523.77.5Tropional
0.450.40.170.60.81.2Calone
Polo sport W
Cool water fem
L’Eaud’Eden
L’Eaud”Issey
Escape for her
New west
for her
%
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Muguet accord
2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol
Florol®
3-(4-tert-butylphenyl)-2-methylpropanal
Lilial®
Name Structure
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Muguet perfume combination
3.31.752.52Hydro xycitronellal
3.27.58.55.53.5Lilial
2.75.675.50.5Florol
FragileJ’adoreDazzling Gold
O ouiXS for her
%
Hydroxycitronellal 58
Physicochemical property
- Boiling point
- Melting point
- Vapor pressure
- Specific gravity
- Refractive index
- Optical rotation
- Flesh point
- Smoke point
- Moisture content
- Viscosity
- pH
- Turbidity
- Color
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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. Kraft P, Bajgrowicz JA, Denis C, Fráter G. Odds and
trends: recent developments in the chemistry of odorants. Angre. Chem. Int. Ed. 39:2980-3010, 2000.
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Thank you for your attention