4 Volatile Oils

8/3/2019 4 Volatile Oils

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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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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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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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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

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