Fragrance Chemistry - Mae Fah Luang...

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


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Frequency of fragrance in products

8

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


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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


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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


2 500 ppb (H2O)

Green, nutty, potato, cocoa, coffee, caramel


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


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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'


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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


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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


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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


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


IUPAC names

O

O

O

O


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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


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


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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

%

56

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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Fragrance Chemistry - Mae Fah Luang...

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