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Nattaya Lourith, Ph.D.
Synthetic Aroma
2
Objectives
To be acknowledged on general chemical syntheses
To be informed on synthetic aroma materials
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Contents
Introduction Overview of organic synthesisTypical reactions in synthetic fragrancesSynthetic aroma materials
Found in cis form in nature, used in perfumes as base note 22
(CH2)12CNH3C H
CH2CN
(CH2)11CHCNH3C H
CH2C=NH
(CH2)11CHCOOHH3C H
CH2C=O
(CH2)11CH2H3C H
CH2C=O
Et2NLi H3O+
H+
Muscone
Used as a fixative and a modifier in high-grade perfumes
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Limonene
OH
O+H2
OH OH
OH
H3O+ HOH
+
-HOH
+O
O
(C6H5)3P=CH2
Limonene is found in most citrus oils. The (+) isomer is found in orange, celery and caraway oils. The (-) isomer is found in pine needle oils. Limonene is used in cosmetics and soaps.
Diels-Alder addition and Wittig reaction
Wagner-MeerweinGeraniolcyclization
24
TerpineneO Cl
Cl ClPOCl3 OH- Na/EtOH
0 oC
α-terpene occurs in savin, coriander and cardamom oils
Lemon-like odor
Used in synthetic oils and technical products
Nattaya Lourith, Ph.D.
25
Found in Siberian pine needle oil both in the (+) and (-) isomers
Faint camphoraceous odor
Used in technical products
Camphene
H H
H CHO+
CHO
H2/Pd-C
CHOAc2O
CHOAcO3
ONaNH2CH3Cl O
1. MeMgBr2. H3O+
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Geraniol
O
COOR
O
COOR
O
COOR
O
O
CH2OH CH2OHOH
CH2OAcOH
CH2OAcOAc OH
(CH2OH)2 1. LiAlH42. H+
1. MeMgBr2. H3O+
Ac2O
OH-
Major component of rose, palmarosa, geranium and citronella oils
Found as glucoside amygdalin in cinnamon bark and leaf oils and almond and apricot oilsPowerful crush bitter almond when freeUsed in cosmetics and soaps
56
Anisaldehyde
Me
OH
Me
OMe
CHO
OMe
Me2SO4/OH- MnO2
Found from anise and fennel oils
Odor of blooming hawthorn
Used in perfumes and soaps
Used in lilac, mimosa, heliotrope and sweet pea blends
Prepare by Williamson methylationof cresol and oxidation with manganese dioxide
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Vanillin
OHOMe
HCN/HCl
OHOMe
CH=N+H2 CHO
OMeOH
HOH
Found in vanilla bean
Strong odor of vanilla
Used to impart a sweet and lasting note to floral and fancy perfumes
Prepare by Gattermann reaction 58
Not found in nature
Odor of hyacinth
Used in perfumes, cosmetics and in hyacinth, jonquil, narcissus, jasmine and lilac blends
Provide top note in floral
Phenelacetaldehyde
OH CHOH2CrO4
Prepare by chromic acid oxidation of phenylethanol
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Cinnamaldehyde
CHO+ RCH2CHO
CHO
ROH-
Found in cassia leaf and bark and cinnamon bark oil
Odor of cinnamon used in perfumes
Prepare via Aldol condensation 60
Cinnamaldehyde derivatives
Leafy C7H15
Jasmine C6H13
Jasmine, lilyC5H11
Green leafC4H9
Spicy, amberC3H7
Spicy C2H5
Cinnamon, coumarin, spicyCH3
Cinnamon H
OrganolepticR
CHO
R
Nattaya Lourith, Ph.D.
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Not found in nature
Odor of floral-green with cucumber-melon
Used in floral such as lily, lilac, peony and magmolia
Cyclamenaldehyde
CHO CH=CCHO CH2CHCHO
EtCHOOH-
H2protect
carbonyl
Me Me
Prepare via Aldolcondensation
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Obtained from Stirlingia latifolia oil
Strong sweet and aromatic odor
Used in floral such as lilac, hawthorn and wisteria
Used in soaps
Acetophenone
R R
COMe
(MeCO)2OAlCl3 Prepare via Friedel-
Craft reaction
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Found in thyme and ajowan oils
White solid with thyme odor
Prepare by hydrogenation reaction followed by Se dehydrogenation
Thymol
O OH OHH2/Pt Se
heat
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Carvacrol
OHSO3HSO3
H2SO4
OH-
heat
Found in majoram, origanum, savory and thyme oils
Used in soaps and dental products
Prepare via Sulfonation reaction
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Anethole
OMe OMe
CHClCH2CH3
OMe
CH=CHCH3
CH3CH2CHOHCl/ZnCl2
OH-
Obtained from anise and funnel seeds
White solid with sweet odor
Used in dental products
Prepare via haloalkylation reaction
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Eugenol
OHOMe
OCH2CH=CH2OMe
OHOMe
CH2CH=CH2
CH2=CHCH2BrOH-
heat
Found in free and glucoside forms in cloves oil
Pale yellow liquid with strong odor
Used in perfumes, soaps and cosmetics
Prepare via Claisen rearrangement
Nattaya Lourith, Ph.D.
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Obtained from nutmeg and ylang-ylang oils
Pleasant odor
Used in floral bouquets and base of carnation scents
Isoeugenol
OHOMe
CH2CH=CH2
OHOMe
CH=CHCH3
1. OH-
2. H+
Prepare via Isomerizationreaction
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Methyleugenol
OHOMe
CH2CH=CH2
OMeOMe
CH=CHCH3
MeI/OH-
Obtained from citronella oil from acacia flowers
Softer odor then eugenol
Used in perfume combination of carnation and oriental as a modifier
Etaspirene® Exp. Pleasures (E. Lauder, 1995)Neocaspirene® Exp. Le monde est beau (Kenzo, 1997)
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Galbanum
α-Dynascone®β-Dynascone®
A fruity, pineapple-type note in Fougère
Exp. Cool water (Davidoff, 1988), Egoïste Platinum (Chanel, 1993)
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The green of leaves
O OCHO
HO(CH2)2OHH
Glycolierral®
An ivy-leaf odor
Exp. J’adore (C. Dior, 1999)
Nattaya Lourith, Ph.D.
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Undecavertol®
The green of leaves
A violet-leaf odor
Exp. Extravagance d’Amarige (Givenchy, 1998), Sunwater (Lancaster, 1997), Escape for Men (C. Klein, 1993) 74
Sea-breeze
Calone 1951®
A marine note
Exp. New West for her (Aramis, 1990), Escape for her (C. Klein, 1991), L’ Eau d’Issey (I. Miyake, 1992), L’Eaud’Eden (Chcharel, 1996), Cool Water fem (Davidoff, 1996), Polo Sport Woman (R. Lauren, 1996)
Hedione® and Magnolione®Exp. Coriandre (Couturier,
1973), Eden (Cacharel, 1994)78
Woody
Firsantal® : a woody-sandal-floral noteExp. Ultra Violet (P.Rabanne, 1990)Firsantol® : a woody-aromatic-musky noteExp. 212 foe men (C. Herrera, 1999)
Nattaya Lourith, Ph.D.
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Woody
Iso E Super®
Exp. Fahrenheit (C.Dior, 1988), Trésor (Lancôme, 1991), Féminité du Bois (Shiseido, 1992), Déclaration (Cartier, 1998)
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Ambery
Spirambrene®
A floral-oriental odor
Exp. Kenzo pour Homme (Kenzo, 1991)
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1. Arctander S. Perfume and Flavor Chemicals (Aroma Chemicals). V. 1. Illinois: Allured; 1994.
2. Gimelli SP. Aroma Science. New York: Micelle Press; 2001.
3. Kraft P, Bajgrowicz JA, Denis C, Fráter G. Odds and trends: recent developments in the chemistry of odorants. Angrew. Chem. Int. Ed. 39:2980-3010, 2000.
4. Nattaya L. Synthetic Aroma material in Aromatic Science 1701351 [Lecture handout]. Chiang Rai: MFU;2007-2010.