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Volatile Oils
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Volatile Oils
odorous principles in various plant parts
evaporate when exposed to air at ordinary
temperature volatile/ethereal/essential- essences or odoriferous constituents of
the plants
colorless when fresh, oxidize and resinify on long
standing and darken glandular hairs/modified parenchyma cells/oil tubes
or vittae/lysigenous or schizogenous passages
insect repellants/attractants
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Volatile Oils Spices
dried, fragrant, aromatic or pungent plant parts that
contain a volatile oil used primarily in food as a seasoning rather than for
nutrition Many volatile oils and spices consist largely of:
Monoterpenoids
Phenylpropanoids (phenols/phenolic ethers) Chemical constituents
terpene derivatives via acetate - mevalonic acid pathway aromatic compounds via shikimic acid -
phenylpropanoid route
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Volatile Oils have characteristic odors high refractive indices
mostly optically active immiscible with water soluble in most organic solvents can be distilled from their natural sources do not consist of glyceryl esters of fatty acids, no permanent grease spot on paper can not be saponified with alkalies do not become rancid vary widely in their chemical composition
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Methods of obtaining volatile oils
Distillation of the plant partsa) water (dried and not subject to injury by boiling)
b) water and steam (dried or fresh that may be injured byboiling
c) direct steam (fresh plant part)
Enzymatic hydrolysis of the glycosides (bitter
almond/mustard) Expression ecuelle method
Enfleurage
Extraction - solvent systems
Destructive (dry) distillation empyreumatic oils
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Medicinal/commercial uses
Inhalations,orally,gargles/mouthwashes,
transdermally aromatherapy
spices, condiments, flavoring agent
carminative, antiseptic, antispasmodic
perfumery [top, middle, base (fixatives- low volatility
and high tenacity; musk, civet, ambergris) notes]
confectionery
cosmetic industry
soap, toiletries, deodorizers, cleaners, polishes,
insecticides
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Volatile Oils
Eleoptene HC portion, liquid (eugenol, eucalyptol, methyl
salicylate) Stearoptenes
oxidized HC portion
usually solid (menthol, thymol, anethole)
characteristic odor or flavor Stereochemistry
determines the type of olfactory response evoked bythe compounds
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Separation of mixtures of compounds involatile oils
low temperature
fractional distillation
fractional crystallization
chromatography
removal by chemical action
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Volatile oils consist largely of:
terpenes (terpenoids)
natural products made up of isoprene units
(biosynthetic building blocks ) = monoterpenes,
sesquiterpenes, diterpenes, triterpenes
phenylpropanoids
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Biosynthesis
Terpenes
Isoprene units
Isopentenyl pyrophosphate +dimethylallyl pyrophosphate
(acetate via - mevalonic acid)
Geranyl pyrophosphate
(acyclic monoterpenes)
isomerized
Neryl pyrophosphate
(cyclic monoterpenes)
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BIOSYNTHESIS
-------------------------------------------------------------Phenylalanine Tyrosine (shikimic acid pathway)
Cinnamic acid + p-hydroxycinnamic acid/p-coumaric acid
Phenylpropanoids
Shikimic acid chorismic acid anthranilic acid tryptophan
prephenic acid
Prephenic acid : phenylpyruvic acid (phenylalanine)
p-hydroxyphenylpyruvic acid (tyrosine)
cinnamic acid direct enzymatic deamination of phenylalanine
p-coumaric acid tyrosine or hydroxylation of cinnamic acid
HYDROCARBON VOLATILE OILS
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Hydrocarbon Volatile Oils Occur in practically all volatile oils
limonene, p-cymene, pinene, sabinene, myrcene, cadinene
Turpentine oil oleoresin from Pinus palustris (Pinaceae) terpenes and pinene counterirritant rectified T.O. expectorant Terpin Hydrate stimulant to mucous membrane - expectorant
Black Pepper unripe fruit pfPiper nigrum (Piperaceae) chavicine sharp taste vol oil- aroma (- caryophyllene, limonene, sabinene, and
pinene), piperine (pungency) and piperettine and a resin aromatic principle (pericarp), pungency (seed)
condiment, stimulant, irritant, febrifuge
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Hydrocarbon Volatile Oils Cubeb/Tailed Pepper
full-grown fruit ofPiper cubeba Piperaceae sabinene, carene, cadinene, cubebin
diuretic, antiseptic, stimulating expectorant, carminative Celery/Kintsay
ripe fruit ofApium graveolens Apiaceae d-limonene, apiin asthma, rheumatic diseases, high blood pressure, emetic, food seasoning
Humulus/Hops
strobiles ofH.lupulus (Moraceae/Cannabinaceae) bitter principles - -acids (humulone) and -acids (lupulone) Humulene sedative, bitter tonic, beer manufacture
Lupulin/Humulin glandular trichomes from strobiles
-myrcene, humulene; bitter tonic
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Alcohol Volatile Oils Acyclic/monocyclic/dicyclic
geraniol, linalool, citronellol Menthol, -terpineol Borneol
Peppermint (American) leaf and flowering top ofMentha piperita (Lamiaceae) menthol, menthone, menthyl acetate carminative, flavor (chewing gum, toothpaste, mouthwashes/
pharmaceuticals stimulant, counterirritant
Menthol (lev/racemic) by refrigeration synthetic racemic- thymol/pinene antipruritic
counterirritant/antiseptic, stimulant,
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Alcohol Volatile Oils Japanese Peppermint Yerba Buena
Mentha arvensis var. piperascens higher in menthol content but inferior in flavor
Menthol combined with camphor and eucalyptus oil in ointments,cough drugs, nasal sprays, inhalants
Cardamom seed ofElettaria cardamomum (Zingiberaceae) cineole, limonene, sabinene
flavor, carminative Coriander Culantro, Uansoy
fruit ofCoriandrum sativum (Apiaceae) linalool (coriandrol), limonene, -pinene, -terpinene, -
cymene
flavor, carminative
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Alcohol Volatile Oils Rose
flowers ofRosa gallica/damascena/alba/centifolia (Rosaceae) geraniol, citronellol, nerol perfume
Orange Flower Neroli Oil flowers ofCitrus aurantium (Rutaceae) linalool, -terpineol, geraniol, geranyl acetate, linalyl acetate,
-pinene, limonene perfume, flavor
Juniper fruit ofJuniperus communis (Cupressaceae) -terpineol, borneol, geraniol, -pinene, -pinene certain varieties of gin, flavor, diuretic, antiseptic
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Alcohol Volatile Oils
Pine oil
by extraction and fractionation/steam distillation of
wood- Pinus palustris (Pinaceae)
-terpineol, methyl chavicol, borneol, fenchol
disinfectant, deodorant
Sandalwood heartwood ofSantalum album (Santalaceae)
, santalols
perfumery
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Aldehyde Volatile Oils Acyclic/cyclic
citral (geranial and neral)/ citronellal/cinnamaldehyde/vanillin
Cinnamon Kanela bark ofCinnamomum loureirii (Saigon)/zeylanicum
(Ceylon)/cassia (Cassia) Lauraceae volatile oil, mannitol, tannin
carminative, flavor Cassia oil leaves and twigs
cinnamic aldehyde, limonene flavoring agent, carminative, pungent aromatic,
antiseptic
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Aldehyde Volatile Oils Lemon Peel
outer yellow rind of the fresh ripe fruit ofCitrus limon (Rutaceae)
flavoring agent, stimulant, stomachic Lemon oil
pressure, sponge process, ecuelle a piquer, machine, distillation
limonene, -pinene, -terpinene, citral (neral and geranial - flavor)
neryl and geranyl acetates full-bodied lemon flavor
flavoring agent (food, cosmetics, liquid cleaners), stimulant,carminative, stomachic, perfume
Terpeneless oils
distillation under reduced pressure (95% terpenes removed)
higher price
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Aldehyde Volatile Oils Bitter Orange Peel
Citrus aurantium aurantiamarin, aurantiamaric acid, aurantin, Vit C
Sweet Orange Peel - Orange oil expression from fresh peel ofCitrus sinensis decanal, limonene flavor
Citronella oil Lemon Grass/Tanglad (Cymbopogon/Andropogon citratus)
steam distillation of leaves Cymbopogon winterianus/nardus(Poaceae) citronellal, citral, geraniol, citronellol; perfume, insect repellant
Hamamelis Water steam distillation of twigs hexenal, acetaldehyde; astringent
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Ketone Volatile Oils
Monocyclic terpene ketones
Menthone
Carvone
Piperitone
Dicyclic ketones
Camphor Fenchone
Thujone
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Ketone Volatile Oils
Camphor Cinnamomum camphora (Lauraceae)
natural camphor
synthetic camphor (pinene)1. pinene to bornyl esters
2. hydrolyzed to isoborneol
3. oxidized to camphor
topical antipruritic, rubefacient, anti-infective,manufacture of plastics
Safe and effective for reducing cough when externallyapplied to chest and throat of young children
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Ketone Volatile Oils
Spearmint leaf and flowering top ofMentha
spicata/viridis/cardiaca (Lamiaceae) taste not followed by a cooling sensation
resin, tannin, volatile oil
flavor, carminative
Spearmint oil (-) carvone, limonene, cineole
flavor, carminative
chewing gum, toothpaste, mouthwash
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Ketone Volatile Oils Caraway oil
fruit ofCarum carvi (Apiaceae) (+) carvone, limonene
fruits for culinary purposes flavor, carminative
Dill fruit ofAnethum graveolens Apiaceae (+) carvone, limonene flavor, carminative
Buchu leaf ofBarosma betulina/crenulata/serratifolia (Rutaceae) volatile oil (pulegone, menthone), diosmin, diosphenol/buchu
camphor diuretic, urinary antiseptic
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Ketone Volatile Oils
Wormwood oil/Absinthe oil leaves and flowering tops ofArtemisia absinthium
(Asteraceae) (+) thujone, camphene, phellandrene, -
caryophyllene
counterirritant
Cedar Leaf Oil Leaves - Thuja occidentalis (Cupressaceae)
(+) thujone, fenchone, -pinene
counterirritant
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Phenol Volatile Oils
present naturally
produced by destructive distillation of plant
products
Ex: Thymol, eugenol, carvacrol, creosol, guaiacol
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Phenol Volatile Oils Clove Clavo/Clavillo
flower buds ofEugenia caryophyllus/caryophyllataMyrtaceae
flavor, carminative Volatile oil (Syzygium aromaticum)
eugenol, eugenol acetate, -caryophyllene, methyl-n-amyl ketone (fresh fruity note/odor)
flavor/spice, toothache remedy, antiseptic,counterirritant, carminative, commercial production ofvanillin
Eugenol dental analgesic
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Phenol Volatile Oils Thyme oil Tremoncillo
flowering plant ofThymus vulgaris/zygis var.gracilisLamiaceae
volatile oil thymol, carvacrol,p-cymene, camphene,limonene
antiseptic
Thymol thyme oil, horsemint oil, ajowan oil
synthetic m-cresol andp-cymene1. freezing temperature2. NaOH solution Na thymol decomposed with acid thymol
antifungal, antibacterial (lotions, creams, ointments)
more powerful than phenol but use is limited by its lowsolubility in water, irritancy and susceptibility to protein
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Phenol Volatile Oils Myrcia oil Bay oil
leaves ofPimenta racemosa Myrtaceae eugenol, myrcene, chavicol perfume
Pimento/Allspice oil Jamaica or Clove Pepper fruit ofPimenta dioica Myrtaceae eugenol, cineole, phellandrene, caryophyllene
Creosote Beechwood creosote wood tar from destructive distillation of wood- Fagus
grandiflora Fagaceae guaiacol, creosol disinfectant, expectorant
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Phenol Volatile Oils Juniper Tar Cade oil
empyreumatic oil from heartwood ofJuniperus oxycedrus
Cupressaceae guaiacol, cresol, cadinene
local antieczema
Pine Tar destructive distillation of wood ofPinus palustris
Pinaceae
phenol, creosol, naphthalene
local antieczema, anti-psoriasis
expectorant
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Phenolic Ether Volatile Oil Nutmeg Myristica
seed deprived of seed coat and arillode ofMyristica fragransMyristicaceae
dried arillode (mace) fixed oil (nutmeg butter), volatile oil (myristicin and safrole,
methoxyeugenol, camphene, terpineol, - pinene, myrcene) flavor, condiment, carminative control diarrhea associated with carcinomas
hallucinogen (large amount- elemicin and myristicin) Anise Aniseed/Matalahuga
fruit ofPimpinella anisum (Apiaceae) volatile oil flavor
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Phenolic Ether Volatile Oil Anise oil
Pimpinella anisum (Apiaceae) Illicium verum (Magnoliaceae/Illiciaceae) anethole, anisaldehyde, chavicol flavor, carminative
Chinese Anise Star Anise/Sanke fruit ofIllicium verum (Magnoliaceae/Illiciaceae) volatile oil (anethole) flavor
Japanese Star Anise - Bastard Star Anise/Shikimmi/Skimmi Illicium religiosum/anisatum shikimic acid (sikimitoxin- (amorphous) and sikimi-
(crystalline), hananomin (toxic)
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Phenolic Ether Volatile Oil Fennel Anis/Haras
fruit ofFoeniculum vulgare (Apiaceae) anethole, fenchone, - pinene, limonene, methyl
chavicol flavor, carminative
Sassafras bark of the root ofSassafras albidum Lauraceae
aromatic, carminative volatile oil (root) safrole (camphor oil, sassafras oil, japanese star anise) showed evidence of being a carcinogen), -pinene,
phellandrene,
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Oxide Volatile Oil Eucalyptus
Blue Gum Leaf/Fever Tree
scythe-shaped leaf ofEucalyptus globulus Myrtaceae requires much water and used for drying up marsh
land
volatile oil (cineole/eucalyptol) free from large
amounts of phellandrene, -pinene industrial purposes piperitone and phellandrene
perfumery geraniol/esters and citronellal
flavor, antiseptic, diaphoretic, expectorant
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Oxide Volatile Oil Cineole/eucalyptol/cajuputol
camphoraceous odor, pungent, cooling, spicy taste1. fractional distillation of eucalyptus oil and freezing of
distillate or treatment of eucalyptus oils with phosphoricacid and decomposition of cineole-phosphoric acid withwater
2. dehydration product of terpin hydrate on treatment withacids
flavor nasal inhalers and sprays for antiseptic and mild
anesthetic action to the nose and throat steam inhalation as stimulating expectorants in
bronchitis, external analgesics, mouthwashes
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Oxide Volatile Oil Cajuput oil
fresh leaves and twigs ofMelaleuca leucadendronMyrtaceae rectified by steam distillation
cajuputol (eucalyptol), terpineol parasiticide, carminative stimulant, diaphoretic
Chenopodium American Wormseed/Alpasotes fruit ofChenopodium ambrosioides var anthelmintica
(Chenopodiaceae) fruits (mature), oil (tops still green and immediately
distilled) ascaridole, cymene, limonene anthelmintic (roundworms)
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Ester Volatile Oil Gaultheria
Wintergreen, Teaberry, Checkerberry, Mountain tea leaves ofGaultheria procumbens Ericaceae methyl salicylate (gaultherin and gaultherase)
Methyl salicylate gaultheria oil/wintergreen oil/betula oil, sweet birch oil produced synthetically (salicylic acid and methyl alcohol) leaves ofG. procumbens, bark ofBetula lenta (Betulaceae) flavor for aromatic cascara sagrada fluidextract, local irritant,
antiseptic, antirheumatic, anti-inflammatory
Lavender fresh flowering tops ofLavandula angustifolia Lamiaceae linalyl acetate, linalool, cineole; perfume
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Ester Volatile Oil Rosemary Romero/Dumero
leaves ofRosmarinus officinalis Lamiaceae bornyl acetate cough, diuretic, gas pain, rheumatism, aromatic bath
Bergamot oil fruit ofCitrus bergamia Rutaceae linalyl acetate, linalool, limonene; perfume (hair tonics)
Pine Needle oil Dwarf Pine Needle oil leaf ofPinus mugo Pinaceae bornyl acetate, , pinene; perfume, flavor
Mustard Oil seed Brassica nigra/juncea Brassicaceae allyl isothiocyanate; rubefacient
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Sesquiterpenoids
Artemisinin/qinghaosu
leaves and flowering tops ofArtemisia annua Asteraceae
treatment of malaria (Plasmodium vivax/falcifarum)
Chamomile German Chamomile/Matricaria
Ginseng of Europe (tea) - flowerheads ofMatricaria
recutita Asteraceae
-bisabolol, -bisaboloxides A and B carminative, spasmolytic, anti-inflammatory
Mansanilya Matricaria chamomilla
insect repellant
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Sesquiterpenoids Feverfew
leaves ofTanacetum parthenium Asteraceae chewing fresh leaves/tablets/capsules
parthenolide (serotonin antagonist) antipyretic, febrifuge, prophylaxis of migraine
Valerian- All Heal Root/Summer Heliotrope rhizome and roots ofValeriana officinalis Valerianaceae valerenic acid, valerenolic acid, acetoxyvalerenolic acid,
valepotriates, bornyl acetate antianxiety, sleep aid
Garlic Bawang/Ajos bulb ofAllium sativum Alliaceae alliin allicin (odor and flavor) (diallylthiosulfinate),
diallyldisulfide/diallyltrisulfide antibacterial, hypertension,
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Diterpenoids Forskolin/colforsin
roots ofColeus forskohlii Lamiaceae therapeutic potential in congestive cardiomyopathy, bronchial
asthma, glaucoma, hypertension Ginkgo
leaves (acetone water extract) ofGinkgo biloba Ginkgoaceae ginkgolides A, B, C, M inhibit platelet activating factor
(increase in blood fluidity and circulation)
peripheral vascular disease Taxol/paclitaxel/Pacific Yew
bark of Taxus brevifolia Taxaceae taxol most promising antineoplastic drugs limited supply