Bài giảng tổng hợp hóa học hương liệu

7 O OH Lilial® 8 Functional groups with therapeutic actions Anti-infectious, immunostimulants Anti-infectious, immunostimulants Anti-infectious, immunostimulants Estrogen-like activity A

Basic fragrance

chemistry I

2

Objectives:

• Basic element

• Chemical functional group of aroma compounds

3

Contents:

• Introduction

• Functional group

4

Flower and Chemistry

• Smell a Flower – The Fragrance is Chemistry

• See a Flower – The Colour is Chemistry

• Touch a Flower – The Structure is Chemistry

Carnation

• Flower

• Eugenol

• Perfume & Cosmetics

Vanilla

• Seed

• Vanillin

• Perfume

7 O

OH

Lilial®

8

Functional groups with therapeutic actions

Anti-infectious, immunostimulants Anti-infectious, immunostimulants Anti-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 aldehydes C10 Alcohols C15 & 20 Alcohols Aldehydes Coumarins Esters Lactones Ketones Oxides Phenols Phenyl methyl ethers C10 Terpenes C15 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 & GUSTATION

Multidisciplinary Fields

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Organic Chemistry

Organic synthesis

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Analytical Chemistry

Physical Chemistry

Artificial nose

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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

Pork fired rice

Cheese pizza

hemoglobin is bright red containing Iron (Fe)

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Organic and Inorganic substances

• Organic – C, H, N, O, P, S

• Inorganic – Metal – Salt

21

Weight & Number

0 Shell -1

Electron

1 Nucleus 0

Neutron

1 Nucleus +1

Proton

Mass Location Charge

Particle

Atomic weight = Proton + Neutron Atomic number = Proton

22

Structure

23

Chemical bonds : Octet rule

24

Chemical bonds : Electronegativity

Chemical bonds

Two or more elements combine to form compound

- Covalent bonds

- Ionic bonds

- Hydrogen bonds

26

Covalent bonds

27

Hydrogen bonds

Fragrance and Chemical functional group

- Hydrocarbon

- Oxygen compounds

- Nitrogen compounds

- Sulfur compounds

- Heterocyclic compounds

- Halogen compounds

Fragrance compound name

Dec Non Oct Hep Hex Pent But Prop Eth Meth

Prefix

10 9 8 7 6 5 4 3 2 1 C

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

Suffix

Functional group

31 32

Structure writing

33

Isomers

34

Isomers

Cis or Z Trans or E

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Isomers

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

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Hydrocarbon

Aliphatic alkane : single bond : CnH2n+2 alkene : double bond : CnH2n alkyne : triple bond : CnH2n-2 cycloalkane : CnH2n

alicyclic : aliphatic cyclic

Aromatic

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 : Aliphatic Alkene

- 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

Isoprene

40

myrcene

Terpene

momoterpene : C10H16

sesquiterpene : C15H24

(one and a half)

Hydrocarbon : Aliphatic

farnesene

Alkyne

- unpleasant, petroleum-like odor

- no application in perfumery

But its derivative recently used as

perfume ingredient give powerful green

character

cycloalkane C n H 2n alicyclic : aliphatic cyclic

Similar odor of those alkane having the same number of carbon

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-dimethylbenzene

ortho-dimethylbenzene

o-dimethylbenzene

1,3-dimethylbenzene

meta-dimethylbenzene

m-dimethylbenzene

1,4-dimethylbenzene

para-dimethylbenzene

Alcohols & Phenols : R-OH

Ethers : R-O-R

Aldehydes : R-CHO Acetals : R-C(OR) 2 Ketones : R-COR

Carboxylic acids : R-COOH

Esters : R-COOR

Lactones : 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

H

C H

H C H

H C H

H C H

H

H

H Pentyl Pentane

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Alcohols & Phenols

Some alcohol of interest to perfumer

NA Creamy mushroom

3-octen-2-ol

1.2 ppb (H2O) Powerful mushroom

1-octen-3-ol

1550 ppb (H2O) Green, grassy and leafy

E-3-hexen-1-ol

70 ppb (H2O) Herbaceous, green, grassy

Z-3-hexen-1-ol

400 ppb (H2O) Green, leafy

E-2-hexanol

NA Fresh green, leafy

Z-2-hexanol

Odor detection threshold Organoleptics

Alcohol

47

Pure phenol is colorless crystal with clean and

antiseptic odor

Phenol was the first antiseptic ever used

Pure phenol is very dangerous cause extremely

painful skin burn

OH

Alcohols & Phenols

O OH

OH

Eugenol

Thymol

Glucoside form in oil of cloves, pale yellow liquid, strong odor Antibacterial, antifungal

Perfumes, Soaps, Cosmetic

Thyme and ajowan oil, white solid, thyme odor

48

Aldehydes

Aldehyde = alcohol dehydrogenatum Latin

= dehydrogenated alcohol English

3.0 ppb (H2O) Vinous fruity, coarse, very

powerful

CH3(CH2)5CHO Heptanal

4.5 ppb (H2O) Fruity green, very powerful

CH3(CH2)4CHO Hexanal

12.0 ppb (H2O) Choking, pungent, fruity, oily

CH3(CH2)3CHO Pentanal

0.7 ppb (H2O) Orange peel, fatty, very powerful

CH3(CH2)6CHO Octanal

9.0 ppb (H2O) Choking, pungent, fruity

CH3(CH2)2CHO Butanal

9.5 ppb (H2O) Choking, suffocating, fruity

CH3CH2CHO Propanal

8.7 ppb (H2O) Choking, vinous, fruity

CH3CHO Acetaldehyde

Odor detection threshold Organoleptics

Formula Aldehydes

Important aldehyde in perfumery = C8-C13

Perfume industry tends to speak of aldehyde C12rather than dodecanal

Acetals

R

O

R

O

H

R O R

O R

O O

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

Ketones

Acetone (aketon German ) rose to ketone

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

Fruity, orange like, floral

CH3CO(CH2)7CH3 Decanone

Fruity, floral, herbaceous

CH3CO(CH2)6CH3

Nonanone

Floral, green fruity, herbaceous

CH3CO(CH2)5CH3

Octanone

Sweet, fruity, spearmint

CH3CO(CH2)4CH3 Heptanone

Ethereal, fruity

CH3CO(CH2)3CH3 Hexanone

Fruity, orange like, waxy, floral

CH3CO(CH2)8CH3 Undecanone

Ethereal, not unpleasant

CH3CO(CH2)2CH3 Pentanone

Ethereal, not unpleasant

CH3COCH2CH3

Butanone

Harsh, ethereal

CH3COCH3

Propanone

Organoleptics Formula

Ketones

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Esters

1.0 ppb (H2O) Ethereal, fruity, buttery

EtOOC(CH2)2CH3 Ethyl butyrate

1.5 ppb (H2O) Strong, fruity, apple

EtOOC(CH2)3CH3

Ethyl valerate

1.0 ppb (H2O) Strong, fruity, wine, apple,

banana, pineapple EtOOC(CH2)4CH3

Ethyl hexanoate

2.2 ppb (H2O) Strong, fruity, wine, cognac

EtOOC(CH2)5CH3

Ethyl

heptanoate

15.0 ppb (H2O) Fruity, wine, sweet,

cognac-apricot EtOOC(CH2)6CH3

Ethyl octanoate

850.0 ppb (H2O) Fatty, oily, cognac, nut

EtOOC(CH2)7CH3

Ethyl nonanoate

10.0 ppb (H2O) Strong, ethereal, fruity, rum

EtOOCEt Ethyl propionate

5000.0 ppb (H2O) Ethereal, sharp, wine-brandy like

EtOAc Ethyl acetate

Odor detection threshold Organoleptics

Formula Esters

52

Cinnamon

• Bark

• Cinnamaldehyde

• Perfume

Cinnamon

• Leaf

• Eugenol

• Vanillin raw material

Citronella

• Leaf

• Citronellol

• Soap & Cosmetics

Clove

• Bud

• Eugenol

• Perfume

56

Cumin

• Seed

• Cuminaldehyde

• Perfume

57

Eucalyptus

• Leaf

• Cineole

• Fixative

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Fennel

• Seed

• Anethole

• Oral care

59

Geranium

• Stem & Leaf

• Geraniol

• Perfume

60

Hyacinth

• Flower

• Benzyl acetate

• Fragrant

Jasmine

• Flower

• Benzyl acetate

• Floral perfume

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Lavender

• Flower

• Linalool

• Perfume & Soap

63

Lemongrass

• Leaf

• Citral

• Soap & Detergent

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Nutmeg

• Seed coat

• i -Camphene

• Oral care

Orange

• Fruit peel

• d -Limonene

• Perfume & Lipstick

Orange

• Flower

• Linalool

• Perfume & Cosmetics

Patchouli

• Leaf

• (-)-Patchoulol

• Perfume

68

Pennyroyal

• Stem

• d -Pulegone

• Soap

69

Peppermint

• Leaf

• i -Menthol

• Oral care

70

Rose

• Flower

• i -Citronellol

• Perfume

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Sandalwood

• Wood & Root

• Santalol

• Fixative

72

Spearmint

• Leaf

• i -Carvone

• Oral care

Star anise

• Fruit

• Anethole

• Perfume

74

Thyme

• Leaf & Flower

• Thymol

• Soap

75

Wintergreen

• Leaf

• Methyl salicylate

• Oral care

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Ylang ylang

• Flower

• Benzyl acetate

• Perfume

References

1 Butler H, editor Poucher’s Perfume, Cosmetics and

Soaps 10thed Dordrecht: Kluwer; 2000.

2 Curtis T, William DG Introduction to Perfumery 2nded

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

Thank you for your attention