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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
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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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Rose oil
Component % of OilThreshold in
ppbOdor Units
x 10-3
Rel. % of odor units
(-)-Citronellol 38 40 9500 4.3C14 - C16 Paraffins 16 - - -Geraniol 14 75 1860 0.8Nerol 7 300 233 0.1Phenethyl alcohol 2.8 750 37 0.016Eugenol methyl ether 2.4 820 29 0.013Eugenol 1.2 30 400 0.18Farnesol 1.2 20 600 0.27Linalool 1.4 6 2300 1(-)-Rose oxide 0.46 0.5 9200 4.1(-)-Carvone 0.41 50 82 0.036Rose furan 0.16 200 8 0.003beta-Damascenone 0.14 0.009 156000 70beta-Ionone 0.03 0.007 42860 19.2
O
CH3
CH3CH3
CH3 CH3
CH3
CH3
O
CH3
CH3 CH3
OH
CH3 CH3
CH3
O
CH3
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The Production of Rose Oil
Nattaya Lourith, Ph.D.
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The Production of Rose Oil
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Organic Synthesis
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Overview of the Organic Synthesis
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Synthesis Aroma material categorized by type of reaction
- Substitution- Addition- Elimination - Rearrangement- Oxidation-Reduction (Redox)
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SubstitutionAlkyl halide SN1 and SN2
RX + OH- ROH + X-
SN1 : R:X R+ +:X-
R+ + Nu- RNu or R+ + Nu RNu+
SN2 : R:X + :Nu- RNu + :X- orR:X + :Nu RNu+:X-
H2O
Slow
FastC-------Xδ+ δ-
:Nu---C---Xδ- δ+ δ-
3° 2° 1° CH3SN1
SN2 12
1. Nucleophilic addition
2. Hydrogenation
CH2 CH2 + Br2 CH2 CH2Br Br
CH2 CH2 Br Br+ CH2 CH2Br
+ Br-
CH2 CH2Br
+ Br- CH2 CH2Br Br
Addition
+ H 2H 2 /P tR C H C H 2 R C H 2 C H 3
Nattaya Lourith, Ph.D.
13
1. Cracking of petroleum hydrocarbon
2. Dehydrohalogenation
3. Dehydration
Elimination
H
OH+ H2O
H
XB:- + + BX + X-
H
H+ H2
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Oxidation and Reduction
Aldehydes are oxidized to carboxylic acids by a variety of oxidizing agents, and it is possible to do some selective reduction reactions
CH4 CH3OH H C H
O
C OH
O
H O C O
--44 --22 00 +2+2 +4+4
Oxidation
Reduction
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Aliphatic compounds- Alcohols - Aldehydes - Ketones - Carboxylic acids- Esters
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AlcoholsRX + OH- ROH + X-
RCH=CH2 RCH2CH2BH2 RCH2CH2OH
RCHO RCH2OLi RCH2OH
RX RMgX RR’R”COMgX RR’R”COH
R2CO R2CHAl(O-i-C3H7)2 R2CHOH
B2H6
LiAlH4 H3O+
H2O2/OH-
Mg
Et2O
R’R”CO H3O+
Al(O-i-C3H7)3 i-C3H7OH
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Aldehydes
RCHX2 RCH(OH)2 RCHO
RCH2OH RCH2OCrO2OH RCHO
RCOX RCHXOH RCHO
OH- -HOH
Cr2O72-
H+
H2/Pd
BaSO4
-HX
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Ketones
RC CR RC(OH)2CH2R RCOCH2R
R2CHOH R2CHOCr2OH R2CO
RMgX R2Cd RR’CO
RLi R2C(OLi)2 R2C(OH)2 R2CO
Hg2+
H2SO4
-HOH
Cr2O72-
H+
CdCl2 R’COX
CO2 H3O+ -HOH
Nattaya Lourith, Ph.D.
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Carboxylic acids
RX RCN RCOOH
RX RMgX RCOOMgX RCOOH
RCH2OH RCOOH
CN- H3O+
Mg
Et2OCO2 H3O+
MnO4-
H+
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Esters
RCOOH RCOOR’ + HOH
RCOOR’ RCOOR” + R’OH
R2CO + HOOOCR’ RCOOR
R’OH
H+
R”O-
R”OH
-R’COO-
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C (CH2)7COOMe(CH2)7COOMeO
O
OC(CH2)7COOMe
(CH2)7COOMeNa
O
O
(CH2)7C=O
(CH2)7CH OH
(CH2OH)2HCl
NaBH4
HOH
HOH
PBr3
HBr
HBr
KOH
H3O+H2/Pd-C O=C (H2C)7(H2C)7
Civetone
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
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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
Rose odor used in perfumes, cosmetics and soaps
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Esterification of geraniol
GeraniumTiglate
Rose, geranium
CaproateRose i-ButyrateRose, applen-ButyrateRose Propionate
Rose, lavender
Acetate Rose leafFormateOrganolepticEster
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Nerol
CHO CH2OH1. LiAlH42. H+
Herbaceous, sagei-ValerateRose, orangeFormateRose, sweeti-ButyrateFloral, leafy, orangen-ButyrateOrange blossom, roseAcetate Rose, orangeFormate
OrganolepticEster
Found in neroli, petitgrain, bergamot and citronella
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Linalool
CHO CHOO
OHH2O2OH-
N2H4
Found in (+) isomer in Bois de sol oil, (-) isomer in Japanese Ho oil
Used in perfumes, cosmetics and soaps
Prepared by the epoxidation of geranial followed by the Wharton reaction 30
Esterification of linalool
Fruity, applei-ValerateLavender i-ButyrateBergamot, fruityn-ButyrateBergamot, peachPropionateFloral, fruityAcetate Citrus, herbalFormate
OrganolepticEster
Nattaya Lourith, Ph.D.
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Citronellol
O 1. Zn/BrCH2COOEt2. H3O+
COOEtHOPTSA
COOEt
OHLiAlH4 OHLiNH2(CH2)2NH2
Found (+)-citronellol in Java citronella oil and (-) isomer in Reunion geranium oil
Rose-like odor, used in perfumes, cosmetics and synthetic rose compositions 32
Esterification of citronellol
Fruity, roseTiglateRose CaproateHoney, herbaceousValerateFruity, rosei-ButyrateFruity, rosen-ButyrateFruity, rosePropionate Citrus, roseAcetate Peach, plum, roseFormate
OrganolepticEster
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Menthol
OH
H
H H
OHH
H
OH
H OH
HH
+ menthol + isomenthol + neomenthol + isoneomenthol
O OHH2/Ni
Powerful odor with cooling effect used in dental products, chewing gums and cigarettes
Prepared by reduction of pulegone 34
Esterification of menthol
Citrus Lactate Fruity, woodyi-ValerateBerry, minty, woodyAcetate
OrganolepticEster
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Citronellal
Cl OH
CHO CHO600 oC HCl OH- MnO2 H2Pd-C
Found (+)-citronellal in rose, lemon and citronella oils, (-) isomer in Java lemon oil
Colorless liquid
Used in perfumes, cosmetics and soaps
Prepared from β-pinene thermal rearrangement and 1,4-addition of HCl 36
HydroxycitronellalCHO
SO3HOH
HO
SO3HOH
HO
CHONaHSO3 H2SO4 NaHCO3
A lily of the valley odor
Used as a base note in lilac and mougetcombinations
Nattaya Lourith, Ph.D.
37
Citral
COOEt+ H
Br OEtOOC
O OHC
OHEtOC=C
CHO+
CHO
EtOCEtO- H+ 1. BrMgC=COEt
2. H3O+
H2Pd-BaSO4
H3O+
A mixture of neral and geranial
Pale yellow liquid, Strong lemon-like odor
Found mainly in lemongrass
Used in perfumes, cosmetics and soaps 38
Carvone
OH OH
ClNOH
OH
NOH OH+EtO-NOCl
Found (+)-carvone in caraway and dill seed oils, (-) isomer in spearmint oil and racemate in gingergrass oil
(+)-Carvone has caraway odor, used in dental and oral preparations
(-)-Carvone has mint odor, used in dental products
Prepared from α-terpineol
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Menthone
Found in pennyroyal and
peppermints oils
A peppermint odor with less cooling effect than menthol
Used to compound synthetic oils
OO O
EtNH(CH2)2COMeEtO-
H2Pd-C
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Piperitone
OMe OMe O
Li/NH3 H3O+
Found (+)-piperitone in Japanese mint oil and (-) isomer in eucalyptus oil
A camphoraceous odor, used in technical products and for the synthesis of menthol
Prepared via Birch reaction
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Pulegone
CHOOAc O O
Ac2OOAc-
1. H+
2. CrO3
Ba(OH)2
Found in lemongrass oil
Isopulegone is found in pennyroyal
Pulegone is used in soaps and dental products
i-pulegone pulegone
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FenchoneCOOEt
O
COOEt
HO COOEt
COOEt
COOEt
COOH
COOH
ZnBrCH2COOEt
PBr3 H2/Pt
O OPb CH3I
Na
Found in fennel seed oil, has a camphoraceous odor
Imparts a pine tone to room sprays and bath preparations
Prepared via a Reformatsky reaction and a Ruczickacyclization
Nattaya Lourith, Ph.D.
43
Benzyl alcohol
CHO
+ HCHO
OH
+ HCOOHOH-
Found free in tuberosa, jasmine, hyacinth and ylang-ylang oil
Prepare by cross Cannizaro reaction
- Faint odor, used in perfumes, cosmetics and soap
- Used in floral oils such as tuberosa, jasmine, gardenia and ylang-ylang
- Used as fixative
44
Phenylethanol
OHHCl/AlCl3
O
Found free in neroli, geranium and rose oils
Found as benzoate or phenylacetate in neroli bigarade and rose oils
- A honey-rose odor alcohol
- Used in perfumes, cosmetics and soaps
Friedel-Crafts reaction with ethylene oxide
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Esterification of Phenylethanol
Fruity, rosei-ValerateFruity, rosei-ButyrateFloral, grapen-ButyrateRose, balsamicPropionate Honey, fruity, roseAcetate
Odor Ester
Balsamic CinnamateFruity, floralAnthranilineHoney, roseBenzoate Green, fruity, floralOctanoateFruity, green, roseHexanoate
Odor Ester
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Cinnamyl alcoholFound as cinnamate ester in oils, balsams
and resin such as styrax and Peru balsam
Free alcohol has hyacinth odor
Used in lily, lilac and hyacinth perfumes
+ CH3CHOCHO
OHOH- LiAlH4
Aldol condensation then hydride reduction
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Esterification of Cinnamyl alcohol
Fruity i-ValerateFruity, balsamici-ButyrateFruity, balsamicn-ButyrateFruity, spicy, balsamicPropionate Floral, balsamicAcetate Green, balsamicFormate
OrganolepticEster
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Benzoic acidFound in anise seed, cinnamon leaves and cloves
White solid used for ester preparation
Widely used as preservative
MgBr COOMgBr COOH
CO2 H+
Carbonation of Grignardcompound then acid hydrolysis
Nattaya Lourith, Ph.D.
49
Salicylic acidFound in anise, cassia, pennyroyal and ylang-ylang oils
White solid used for ester preparation
Used as a preservative
OH OHCOOH
1. CO2/OH-
2. H+Prepare via Kolbe synthesis
50
Cinnamic acid
CHO+ BrCH2COOEt
COOEt COOHZn H+
Found in styrax oil, cassia and basil
White solid used for ester preparation
Prepare via Reformatsky reaction
51
Phenylacetic acid
CH2Cl CH2CNCN-
CH2COOHH+
Found free and in ester derivative in Japanese mint neroli bigarade oils
Sweet, floral and honey-like odor
Used in perfumes and soaps
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Esterification of Phenylacetic acid
Honey, sweetAllylHoney, wine, rosei-PropylHoney, apricot, rosePropylHoney, sweetEthyl
Honey, sweet, jasmine
Methyl OrganolepticEster
Honey, clove, florali-EugenylWoody, musty, greenMethoxyRose, green, wineHexylHoney, muskyi-Butyl Honey, roseButyl
OrganolepticEster
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Anthranilic acid
NH
O
OCOO-
NH2 NH2
COOHH+Br2/OH-
Found as methyl ester in neroli bigarade oil and jasmine, tuberosa, gardenia flower oils and orange, mandarin and bergamot leaves
Prepare via Hofmann rearrangement of phthalimide in 85% yield
54
Esterification of Anthranilic acid
Fruity, floral, irisPhenethylOrange, floralLinalylMild, sweet, plumButyl Fruity, grape, floralEthyl Orange blossomMethyl
OrganolepticEster
Nattaya Lourith, Ph.D.
55
Benzaldehyde
CH3 CHO1. CrO2Cl22. HOH Prepare via
oxidation reaction
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
57
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
59
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.
61
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
62
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
63
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
64
Carvacrol
OHSO3HSO3
H2SO4
OH-
heat
Found in majoram, origanum, savory and thyme oils
Used in soaps and dental products
Prepare via Sulfonation reaction
65
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
66
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.
67
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
68
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
Prepare by Williamson methylationof eugenol
69
Anapear®
A fruity-green pear note
Exp. Emporio Armani Elle (G. Armani, 1998)
Fruity
70
iPrHHMeHNeocaspirene®MeMeHHEtEtaspirene®R5R4R3R2R1
Blackcurrant
Etaspirene® Exp. Pleasures (E. Lauder, 1995)Neocaspirene® Exp. Le monde est beau (Kenzo, 1997)
71
Galbanum
α-Dynascone®β-Dynascone®
A fruity, pineapple-type note in Fougère
Exp. Cool water (Davidoff, 1988), Egoïste Platinum (Chanel, 1993)
72
The green of leaves
O OCHO
HO(CH2)2OHH
Glycolierral®
An ivy-leaf odor
Exp. J’adore (C. Dior, 1999)
Nattaya Lourith, Ph.D.
73
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)
75
Watermelon
Melonal®
A watermelon note
Exp. Allure (Chanel, 1996) 76
Rose
Doremox® and Phenoxanol® or Mefrosol®
Exp. Birmane (Van Cleef & Arpels, 1999), Bvlgari E.D.P. (Bulgari, 1994)
77
Jasmine & Magnolia
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.
79
Woody
Iso E Super®
Exp. Fahrenheit (C.Dior, 1988), Trésor (Lancôme, 1991), Féminité du Bois (Shiseido, 1992), Déclaration (Cartier, 1998)
80
Ambery
Spirambrene®
A floral-oriental odor
Exp. Kenzo pour Homme (Kenzo, 1991)
81
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.
References
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Thank youfor your attention
