Volatile Oils

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

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 Monoterpenoids Phenylpropanoids (phenols/phenolic ethers)

Many volatile oils and spices consist largely of:

Chemical constituents

terpene derivatives via acetate - mevalonic acid pathway aromatic compounds via shikimic acid phenylpropanoid route

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

Methods of obtaining volatile oils

Distillation of the plant parts
a) water (dried and not subject to injury by boiling) b) water and steam (dried or fresh that may be injured by boiling 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

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

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 by the compounds

Separation of mixtures of compounds in volatile oils

low temperature fractional distillation fractional crystallization chromatography removal by chemical action

 Volatile oils consist largely of:

terpenes (terpenoids)
natural products made up of isoprene units (biosynthetic building blocks ) = monoterpenes, sesquiterpenes, diterpenes, triterpenes

phenylpropanoids

Biosynthesis
Terpenes Isoprene units

Isopentenyl pyrophosphate + dimethylallyl pyrophosphate (acetate via - mevalonic acid)

Geranyl pyrophosphate (acyclic monoterpenes) isomerized

Neryl pyrophosphate (cyclic monoterpenes)

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

Hydrocarbon Volatile Oils

Occur in practically all volatile oils Turpentine oil
limonene, p-cymene, pinene, sabinene, myrcene, cadinene oleoresin from Pinus palustris (Pinaceae) terpenes and pinene counterirritant rectified T.O. expectorant Terpin Hydrate stimulant to mucous membrane - expectorant

Black Pepper

unripe fruit pf Piper 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

Hydrocarbon Volatile Oils

Cubeb/Tailed Pepper
full-grown fruit of Piper cubeba Piperaceae sabinene, carene, cadinene, cubebin diuretic, antiseptic, stimulating expectorant, carminative ripe fruit of Apium graveolens Apiaceae d-limonene, apiin asthma, rheumatic diseases, high blood pressure, emetic, food seasoning strobiles of H.lupulus (Moraceae/Cannabinaceae) bitter principles - -acids (humulone) and -acids (lupulone) Humulene sedative, bitter tonic, beer manufacture glandular trichomes from strobiles -myrcene, humulene; bitter tonic

Celery/Kintsay

Humulus/Hops

Lupulin/Humulin

Alcohol Volatile Oils

Acyclic/monocyclic/dicyclic
geraniol, linalool, citronellol Menthol, -terpineol Borneol

Peppermint (American)

Menthol (lev/racemic)

leaf and flowering top of Mentha piperita (Lamiaceae) menthol, menthone, menthyl acetate carminative, flavor (chewing gum, toothpaste, mouthwashes/ pharmaceuticals stimulant, counterirritant by refrigeration synthetic racemic- thymol/pinene antipruritic counterirritant/antiseptic, stimulant,

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

Coriander Culantro, Uansoy

seed of Elettaria cardamomum (Zingiberaceae) cineole, limonene, sabinene flavor, carminative fruit of Coriandrum sativum (Apiaceae) linalool (coriandrol), limonene, -pinene, -terpinene, cymene flavor, carminative

Alcohol Volatile Oils

Rose
flowers of Rosa gallica/damascena/alba/centifolia (Rosaceae) geraniol, citronellol, nerol perfume flowers of Citrus aurantium (Rutaceae) linalool, -terpineol, geraniol, geranyl acetate, linalyl acetate, -pinene, limonene perfume, flavor fruit of Juniperus communis (Cupressaceae) -terpineol, borneol, geraniol, -pinene, -pinene certain varieties of gin, flavor, diuretic, antiseptic

Orange Flower Neroli Oil

Juniper

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 of Santalum album (Santalaceae) , santalols perfumery

Aldehyde Volatile Oils

Acyclic/cyclic Cinnamon Kanela
citral (geranial and neral)/ citronellal/cinnamaldehyde/ vanillin bark of Cinnamomum loureirii (Saigon)/zeylanicum (Ceylon)/cassia (Cassia) Lauraceae volatile oil, mannitol, tannin carminative, flavor cinnamic aldehyde, limonene flavoring agent, carminative, pungent aromatic, antiseptic

Cassia oil leaves and twigs

Aldehyde Volatile Oils

Lemon Peel
outer yellow rind of the fresh ripe fruit of Citrus 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

Aldehyde Volatile Oils

Bitter Orange Peel Sweet Orange Peel - Orange oil
Citrus aurantium aurantiamarin, aurantiamaric acid, aurantin, Vit C expression from fresh peel of Citrus sinensis decanal, limonene flavor Lemon Grass/Tanglad (Cymbopogon/Andropogon citratus) steam distillation of leaves Cymbopogon winterianus/nardus (Poaceae) citronellal, citral, geraniol, citronellol; perfume, insect repellant steam distillation of twigs hexenal, acetaldehyde; astringent

Citronella oil

Hamamelis Water

Ketone Volatile Oils

Monocyclic terpene ketones
Menthone Carvone Piperitone

Dicyclic ketones
Camphor Fenchone Thujone

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 externally applied to chest and throat of young children

Ketone Volatile Oils

Spearmint
leaf and flowering top of Mentha 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

Ketone Volatile Oils

Caraway oil
fruit of Carum carvi (Apiaceae) (+) carvone, limonene fruits for culinary purposes flavor, carminative

Dill

Buchu

fruit of Anethum graveolens Apiaceae (+) carvone, limonene flavor, carminative leaf of Barosma betulina/crenulata/serratifolia (Rutaceae) volatile oil (pulegone, menthone), diosmin, diosphenol/buchu camphor diuretic, urinary antiseptic

Ketone Volatile Oils

Wormwood oil/Absinthe oil
leaves and flowering tops of Artemisia absinthium (Asteraceae) (+) thujone, camphene, phellandrene, caryophyllene counterirritant

Cedar Leaf Oil

Leaves - Thuja occidentalis (Cupressaceae) (+) thujone, fenchone, -pinene counterirritant

Phenol Volatile Oils

present naturally produced by destructive distillation of plant products Ex: Thymol, eugenol, carvacrol, creosol, guaiacol

Phenol Volatile Oils

Clove Clavo/Clavillo
flower buds of Eugenia caryophyllus/caryophyllata Myrtaceae flavor, carminative eugenol, eugenol acetate, -caryophyllene, methyl-namyl ketone (fresh fruity note/odor) flavor/spice, toothache remedy, antiseptic, counterirritant, carminative, commercial production of vanillin dental analgesic

Volatile oil (Syzygium aromaticum)

Eugenol

Phenol Volatile Oils

Thyme oil Tremoncillo
flowering plant of Thymus vulgaris/zygis var. gracilis Lamiaceae volatile oil thymol, carvacrol, p-cymene, camphene, limonene antiseptic thyme oil, horsemint oil, ajowan oil synthetic m-cresol and p-cymene

Thymol

more powerful than phenol but use is limited by its low solubility in water, irritancy and susceptibility to protein

1. freezing temperature 2. NaOH solution Na thymol decomposed with acid thymol antifungal, antibacterial (lotions, creams, ointments)

Phenol Volatile Oils

Myrcia oil Bay oil
leaves of Pimenta racemosa Myrtaceae eugenol, myrcene, chavicol perfume Jamaica or Clove Pepper fruit of Pimenta dioica Myrtaceae eugenol, cineole, phellandrene, caryophyllene wood tar from destructive distillation of wood- Fagus grandiflora Fagaceae guaiacol, creosol disinfectant, expectorant

Pimento/Allspice oil

Creosote Beechwood creosote

Phenol Volatile Oils

Juniper Tar Cade oil
empyreumatic oil from heartwood of Juniperus oxycedrus Cupressaceae guaiacol, cresol, cadinene local antieczema

Pine Tar
destructive distillation of wood of Pinus palustris Pinaceae phenol, creosol, naphthalene local antieczema, anti-psoriasis expectorant

Phenolic Ether Volatile Oil

Nutmeg Myristica
seed deprived of seed coat and arillode of Myristica fragrans Myristicaceae 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) fruit of Pimpinella anisum (Apiaceae) volatile oil flavor

Anise Aniseed/Matalahuga

Phenolic Ether Volatile Oil

Anise oil
Pimpinella anisum (Apiaceae) Illicium verum (Magnoliaceae/Illiciaceae) anethole, anisaldehyde, chavicol flavor, carminative

Chinese Anise Star Anise/Sanke

Japanese Star Anise - Bastard Star

fruit of Illicium verum (Magnoliaceae/Illiciaceae) volatile oil (anethole) flavor Anise/Shikimmi/Skimmi Illicium religiosum/anisatum shikimic acid (sikimitoxin- (amorphous) and sikimi(crystalline), hananomin (toxic)

Phenolic Ether Volatile Oil

Fennel Anis/Haras
fruit of Foeniculum vulgare (Apiaceae) anethole, fenchone, - pinene, limonene, methyl chavicol flavor, carminative bark of the root of Sassafras albidum Lauraceae aromatic, carminative volatile oil (root) safrole (camphor oil, sassafras oil, japanese star anise) showed evidence of being a carcinogen), -pinene, phellandrene,

Sassafras

Oxide Volatile Oil

Eucalyptus
Blue Gum Leaf/Fever Tree scythe-shaped leaf of Eucalyptus 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

Oxide Volatile Oil

Cineole/eucalyptol/cajuputol
camphoraceous odor, pungent, cooling, spicy taste
1. fractional distillation of eucalyptus oil and freezing of distillate or treatment of eucalyptus oils with phosphoric acid and decomposition of cineole-phosphoric acid with water 2. dehydration product of terpin hydrate on treatment with acids

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

Oxide Volatile Oil

Cajuput oil
fresh leaves and twigs of Melaleuca leucadendron Myrtaceae rectified by steam distillation cajuputol (eucalyptol), terpineol parasiticide, carminative stimulant, diaphoretic

Chenopodium American Wormseed/Alpasotes

fruit of Chenopodium ambrosioides var anthelmintica (Chenopodiaceae) fruits (mature), oil (tops still green and immediately distilled) ascaridole, cymene, limonene anthelmintic (roundworms)

Ester Volatile Oil

Gaultheria
Wintergreen, Teaberry, Checkerberry, Mountain tea leaves of Gaultheria procumbens Ericaceae methyl salicylate (gaultherin and gaultherase) gaultheria oil/wintergreen oil/betula oil, sweet birch oil produced synthetically (salicylic acid and methyl alcohol) leaves of G. procumbens, bark of Betula lenta (Betulaceae) flavor for aromatic cascara sagrada fluidextract, local irritant, antiseptic, antirheumatic, anti-inflammatory

Methyl salicylate

Lavender

fresh flowering tops of Lavandula angustifolia Lamiaceae linalyl acetate, linalool, cineole; perfume

Ester Volatile Oil

Rosemary Romero/Dumero
leaves of Rosmarinus officinalis Lamiaceae bornyl acetate cough, diuretic, gas pain, rheumatism, aromatic bath fruit of Citrus bergamia Rutaceae linalyl acetate, linalool, limonene; perfume (hair tonics)

Bergamot oil

Pine Needle oil Dwarf Pine Needle oil Mustard Oil

leaf of Pinus mugo Pinaceae bornyl acetate, , pinene; perfume, flavor

seed Brassica nigra/juncea Brassicaceae allyl isothiocyanate; rubefacient

Sesquiterpenoids
Artemisinin/qinghaosu
leaves and flowering tops of Artemisia annua Asteraceae treatment of malaria (Plasmodium vivax/falcifarum)

Chamomile German Chamomile/Matricaria

Ginseng of Europe (tea) - flowerheads of Matricaria recutita Asteraceae -bisabolol, -bisaboloxides A and B carminative, spasmolytic, anti-inflammatory

Mansanilya Matricaria chamomilla

insect repellant

Sesquiterpenoids
Feverfew
leaves of Tanacetum parthenium Asteraceae chewing fresh leaves/tablets/capsules parthenolide (serotonin antagonist) antipyretic, febrifuge, prophylaxis of migraine

Valerian- All Heal Root/Summer Heliotrope

Garlic Bawang/Ajos

rhizome and roots of Valeriana officinalis Valerianaceae valerenic acid, valerenolic acid, acetoxyvalerenolic acid, valepotriates, bornyl acetate antianxiety, sleep aid bulb of Allium sativum Alliaceae alliin allicin (odor and flavor) (diallylthiosulfinate), diallyldisulfide/diallyltrisulfide antibacterial, hypertension,

Diterpenoids
Forskolin/colforsin
roots of Coleus forskohlii Lamiaceae therapeutic potential in congestive cardiomyopathy, bronchial asthma, glaucoma, hypertension leaves (acetone water extract) of Ginkgo biloba Ginkgoaceae ginkgolides A, B, C, M inhibit platelet activating factor (increase in blood fluidity and circulation) peripheral vascular disease bark of Taxus brevifolia Taxaceae taxol most promising antineoplastic drugs limited supply

Ginkgo

Taxol/paclitaxel/Pacific Yew