Volatile oils Definition It is a distilled oils obtained from plant tissue or animal sources.

. They are widely used in perfumes, flavoring and medicines. Their chemical composition differs, for example, terpenes, aldehydes, ketons or phenols, oxygen, sulfur, nitrogen.

Volatile Oils Volatile Hydrocarbons not leave filter paper Non-greasy On storage Not rancid but rather resinify

Fixed Oils Non-volatile Triglycerides leave permanent paper Greasy On storage rancid upon exposure to O2

permanent stain on stain on filter

Kinds of Essential Oils

The principal components of essential oils are terpenes and aromatic compounds.

Why do plants produce essential oils? Attraction effect To insects, birds and other animals for pollination and seed dispersal. Repellant effect Plants produce offensive odors or bitter substances to repel pests or predators, or inhibit the growth of molds or harmful bacteria. (Protection against insects and fungi).

Characters of volatile oils 1.Physical characters: Colorless volatile liquid Have high refractive index and optically active Immiscible with water Soluble in organic solvent Resinification when storage due to darken in color when exposed to light

2.Chemical characters: It is a mixture of hydrocarbons and oxygenated compounds (such as alcohol, ketons, aldehydes, phenol, esters). Some oils consists of one main component as oil of clove (eugenol). oil of menthe (menthol). The properties of the volatile oils are determined by the number of isoprene units. Terpenes and terpenoides are the primary constituents of the essential oils of many types of plants and

What are terpenes ? Terpenes are defined as natural products whose structures may be divided into isoprene units.

 Hemiterpenes: consists of a single isoprene units have the molecular formula C5H8 Monoterpenes: consists of a two isoprene units have the molecular formula C10H16 Sesquiterpenes: consists of a three isoprene units have the molecular formula C15H24 Diterpene: consists of a four isoprene units have the molecular formula C20H32 Sesterterpenes: consists of a five isoprene units have the molecular formula C H

Classes of Terpenes present in V.O.: A.Monoterpenes 1.Acyclic. 2.Monocyclic. 3.Bicyclic. 4.Aromatic. B.Sesquiterpenes 1.Monocyclic. 2.Bicyclic. C.Oxygenated hydrocarbons: (oxygenated terpenes) e.g. alcohols, esters, phenols, oxides, peroxides, aldehydes and ketones.

Chemical constituents and odour of volatile oils According to the major constituents, volatile oils acquired different odour as: Fruity odors of ester and lactones Pleasant odor of ketones Bitter almond odor of nitrile

Chemical constituents and action Sesquterpene hepatic and glandular stimulant, anti-inflammatory, antiallergic and nasal decongestant. Monoterpene hydrocarbon antiviral, stimulant, irritant and immunostimulant. Esters spasmolytic, fungicidal, soothing to the skin, antiinflammatory. ketones cell regenerative, mucolytic and neurotoxic. Aldehyde sedative, antiinflammatory, antiviral and relaxing.

Pharmacological importance of volatile oils: 1.Antiseptic and preservative as Lavender, thyme, clove 2.Antispasmodic as Anise, fennel, menthe, chamomile 3.Sedative as clove 4.Irritating agent , externally increase in capillary blood flow as eucalyptus. Internally 5.Stimulates mucus cell , so used as

Medicinal uses
As infusion or separated volatile oils and their isolates by inhalation or orally as gargles Local stimulants Carminatives Mild antiseptic Bacteriostatics Local irritants Anthelmentics Local analgesic In powder form used as spices and condiments in food to impart aroma and flavor and act as preservative In perfume industries , cosmetic preparation Insecticides

Preparation of volatile oils:

Methods
Distillation .Water dist Water and steam .dist .Steam dist Expression Sponge method Scarification Rasping process Machines Extraction Volatile solvent Non-volatile solvent

Methods for preparation of Volatile Oils: 1.Distillation. 2.Scarification and expression. 3.Solvent extraction. 4.Enzymatic hydrolysis of glycosides.

1. Distillation Methods Principle: When two immiscible liquid are heated they will boil at a temperature below the boiling point of either one. Types of distillation: A.Simple steam distillation (waterdistillation). B.Saturated stem distillation (water and steam).

A. Simple steam distillation (water distillation): 1.Immersing the plant directly in a container filled with water, then boiled. 2.Heterogeneous vapors are condensed on a cold surface and collected in a special receiver. 3.Oil separates from water on the bases of difference in density and immiscibility. Cohobation: is the return of the aromatic water to still

19

B. Saturated stem distillation: 1.Saturated stem. 2.The plant not contact with water. 3.Stem pressure and temperature could be modified according to the composition of the oil. Thermolabile as esters need lower pressure and temperature. High boiling point as sesquiterpenoids need higher

B. Scarification and expression: It based on puncturing and/or squeezing of the plant material to liberate the oil. It is used for heat sensitive oils which are present in large amounts in outer peels of fruits as citrus fruits.

Preparation and purification of oil The peel consist of two parts Outer part: colored, rich in waxes and pigments and oil glands. Inner part: white, formed of pectin and cellulose. The method includes: I. Squeezing Methods. II.Scarification (Ecuelle - a - piquer method). III.Expression Method.

I. Squeezing Methods a) Squeezing with water: 1. Squeezing of the peel under stream of water, yield emulsion of oil, water, pectin, cellulose, pigment and wax. 2. Removal of water, pectin and cellulose by centrifugation. 3. Removal of wax by strong cooling, followed by filtration or decantation.

b) Sponge Method: 1. Fruits are washed, cut into halves and fleshy part removed. 2. Peels are soaked in water and pressed between a convex projection and a sponge. 3. Saturated sponge is squeezed in vessel and emulsion centrifuged and cooled.

II. Scarification (Ecuelle - a - piquer method) Based on puncturing (scarifying ) the surface of whole fruits Instrument used is funnel-shaped, consisting of a shallow bowl with a tubular projection at the center. The bowl-like part bears internally numerous pins long enough to scarify the oil glands and release

III.Expression Method 1. Removing the outer layer of the peel, collecting in special bags followed by strong pressing. 2. Oil obtained is collected, left to stand, decant, and filtered.

Machine processes It based on whole fruits are charged into machines in which the peels are removed, sprayed with water, squeezed or pressed and oil collected through wool filters

C. Extraction methods
It is used for preparation of delicate flower oils such as Jasmine, which contain either Small amounts of oils. Oils which decompose by heat. According to the solvent used they classified into: Non- volatile solvent extraction Volatile solvent extraction

Volatile oils

Hydrocar bon

Alcohol Monohhy dric e.g. Thymol, Carvacro ,l Anisol

Phenols and phenolic ethers Dihydric e.g. Eugenol isoeugen ol Trihydric Myristin isomyrist in Tetrahyd ric Parsely camphor

Aldehyd and ketones

Esters

Oxide & Peroxide s Containi ng nitrogen e.g. Anthranil ate

Acyclic

Alicyclic

Aromatic

Aliphatic

Alicyclic

Aromatic Benzyl alcohol

Aldehyde s

Ketonesc

Ester of aliphatic E,geranyl acetate

Aromatic e.g Benzyl benzoate

Oxide

Peroxide

Mono e.g Myrecen e Ocimene Sesquiter pene e.g. Farnecen e

Bicycli c

MonocM enthol

Aliphatic Acyclic e.g Citronell ol, Citral Alicyclic e.g. Perillalde hyde Aromatic e.g Benzalde hyde,Van illin

Acyclic e.g aceton

Monoter pene e.g 1,8cineole Sesquiter pene e.g. Bisabolol

Monoter pene

Bicyclic l

Alicyclic

3,6 membere d ring e.g Thajone, Carvone Sesquiter pene e.g Cadinene s Tricyclic e.g Santalen e Mono e.g. Limonen e

Monoter pene Borneol

Bicyclic e.g. Camphor ,Fenchon e

Sesquiter Carotol

Aromatic

Tricyclic Santalol

Volatile Oils

Hydrocarbon Alcohosl

&Phenols &Aldehyde Phenolic Ketones ethers

Esters

& Oxides Preoxides

Hydrocarbon .V.O

Acyclic

Alicyclic

Aromatic

Monoterpine e.g. Myrecene Ocimene Sesquiterpene e.g. Farnesene

Mono Limonene

Bicyclic

Tricyclic e,.g. Santtalene

Monoterpene

membered ring 3,6 e.g. Thajane carane membered ring 4,6 e.G pinane Sesquiterpene e.g. naphthalene derivative cadinene

Alcohol .V.O

Aliphatic

Alicyclic

Aromatic Benzyl alcohol

Saturatedd

Unsaturated

Monocyclic e.g. Menthol

Bicyclicl

Tricyclic Sesquterpenoid Santalol

Monoterpene Borneol

Sesquiterpene Carotol

Phenols and phenolic componds

Monohhydric . e.g Thymol Carvacrol Anisol nathole9 Anise camphor0

Dihydric e.g. Eugenol Isoeugenol

Trihydric Myristin

Tetrahydric Parsely apiole Parsley camphor

Aldehyd and ketones

Aldehydes

Ketonesc

Aliphatic Acyclic e.G citronellol citral

Alicyclic . e.g Perill aldehyde

Aromatic e.g benzaldehyde Salicylaldehyde Vanillin

Alicyclic

Aromatic

Acyclic e.g. Acetone

Monocyclic e.g.carvone Menthone

Bicyclic e.G Fenchone Camphore

Esters

Ester of aliphatic e.g. geranyl acetate Benzyl acetate

Aromatic e.g Benzyl salicylate Methyl salicylate

Containing nitrogen e.g methyl anthranilate

Oxide & Peroxi

Oxide

Peroxide

Monoterpene - e.g 1,8

Sesquiterpene . e.g

Hydrocarbon V. O.
Acyclic, Monoterpene Myrcene and Ocimene Occurrence: in Lemon grass, Cympobogon Isolation: By fractional distillation, Purification by H2O soluble phenate with NaOH non- phenolic fraction (insoluble part) fractional distillation.

Detection of Myrecene in the presence of Ocimene: Myrecene with Potassium permanganate in acetone Succinic acid + Lead 1. Myrecene (Lead succinate) needle crystals. 2. Ocimene (Lead succinate) rhomboidal crystals.

Sesquiterpene

Farnesene Occurrence: Humulous lupulus Preparation: by fractional distillation. Uses: flavoring agent

Monocyclic, Alicyclic Hydrocarbon

Limonene Occurrence: in Orange Preparation: by fractional distillation. Uses: Flavoring agent.

Alicyclic, bicyclic monoterpene hydrocarbon -Pinene Occurrence: coniferous oil, lemon, coriander Isolation: 1.By fractional distillation. 2.By precipitation as nitroso chloride crystal then aniline -pinene. Uses: Manufacture of borneol and camphor. Mucolytic in cough mixture.

Alicyclic, monocyclic, sesquiterpene hydrocarbon Zingiberene Occurrence: Ginger Isolation: 1.By fractional distillation under vacuum. Test: Zingiberene + Hydrochloric acid crystal of dihydrochloride .

Alicyclic bicyclic sesquiterpene hydrocarbon Azulene (coloured H.C.) e.g. Chamazulene Test: Azulene + mineral acid ( H2SO4) Crystalline derivatives, then decompose by water. Uses Anti-inflammatory - Cosmetic preparation

Aromatic hydrocarbon P-cymene Occurrence: lemon, lavander Isolation: by fractional distillation. Purification from terpenoid by oxidation with cold dil. KMnO4. From limonene or pinene by dehydration, heating with sulphur p-cymene Test: With Potassium permanganate crystal of P hydroxyisopropyl benzoic acid.

Alcohols
Preparation 1. By additive products: using Cacl2 solid, regeneration by water, ext. with ether or benzene. 2. Chromatography. 3. Derivatization: depending upon the presence of functional alc. gp., addition reaction as oxidation, halogenation, hydration for unsaturated as borneol & geraniol 4. Estrification using either: 1- Phthalic anhydride. 2- Boric acid 1ry are more react than 2ry, 3ry not react 3- Succenic anhydride. 5. Dehydration: 3ry more react then 2ry, 1ry resistant except geraniol using ZnCl2.

Acyclic terpene alcohol Citronellol Occurrence: Oil of rose and citronella. Preparation: 1.By fractional distillation of the hydro distilled oil. 2.Semi synthetically from geraniol or nerol by hydrogenation. Uses: In Cosmetic preparation.

Geraniol and Nerol Occurrence: Geraniol In oils of palme rosa, rose, geranium. Nerol In oils of Neroli, bergamot. Preparation: Nerol is difficult to be obtained in a pure form. Geraniol formed a solid derivatives with calcium chloride , while nerol does not form a complex. Geraniol heated with dehydrating agent, diterpen Uses: In perfume, cosmetic preparation.

Linalool Occurrence: In oil of Lavander , Lemon, Rose, Preparation: Fractional distillation Heating with glacial acitic acid -------mixture of geraniol, nerol and terpeniol With chromic acid -------------- citral With halogen acids ---------- Linalyl derivative (linalyl chloride) Uses: In perfume, cosmetic preparation

Alicyclic terpene alcohol

Alicyclic Monocyclic Monoterpene alcohol Menthol Occurrence: In oil of peppermint Preparation: Naturally: From oils by cooling and deposited crystals by centrifuge. Synthesis: Catalytic reduction of thymol using cupper chromate. Test of identity Crystals + conc. Sulphuric acid + vanillin sulphuric reagent ----orange yellow color + water -------violet Crystals + glacial acetic acid + three drops of conc. Sulphuric acid + one drop of conc. Nitric acid ----no green or bluish color (thymol gives green color) Uses : Antiseptic, Counter irritant, Carminative, gastric sedative, Flavoring agents in mouthwashes & toothpastes

Alicyclic bicyclic monoterpene alcohol

Borneol, Isoborneol Source: Nutmeg, lavender, coriander Preparation: By fractional dist, Purification by acidphethalate Synthesis: 1.From -pinene + HCL gas at -10 o pinene HCL, Isomerization bornyl chloride + KOH borneol 2.From camphor using Na amalgam in alc.

Separation of Borneol and Camphor: Phethalic anhydride with NaOH Sod. Salt which soluble in water, extract with org. solvent camphor in org. solvent and Sodium Salt of borneol in aq. Separation of Mixture Of -pinene, borneol and camphor: 1. -Pinene by fractional distillation. 2. Camphor by oxime. 3. Borneol by acid phthalate ester. Uses Sedative, Antiseptic, Counter irritant and room sprays.

Aromatic alcohol -Benzyl alcohol (low volatility) Source: Jasmin, balsam Preparation By fractional dist -Bad storage bitter almond odor + crystal of benzoic acid Test Oxidation with chromic acid + H2SO4 benzoic acid Uses Perfume and Cosmetic

Phenols and phenolic esters: Uses: Antiseptic, germicidal, Properties: acidic, unstable, sol. In alkali. With FeCl3 blue, violet color With Br bromo derivative Preparation: By cooling. By shaking the oil with dil. KOH

Monohydric phenols

1-Thymol 2- Anethol ( Anise camphor) Source: F. Labiatae Anise, Fennel Preparation: Cooling if in large amounts. Fractional distillation. Uses: Flavoring, cosmetic, mouth wash gargle Tests: + KMnO4 -----P FeCl3+ H2SO4---blue

 Synthesis of Thymol 1- Menthone + Bromin/quinolin Thymol 2- Piperitone Thymol Synthesis of Anethol Alc. anisole + propionald/ Hcl, H2SO4/ pyridine Anethol

Dihydric phenol Eugenol (pale yellow oily liquid) Source: Clove, Cinnamon, Nutmeg Preparation: Oil + aq. NaOH , ext. with ether, Phenolic insol. Salt, acidify, then stem distillation or ext. with ether Test:
with alc. Fecl3 with aq. FeCl3 with KOH blue grayish yellow needle crystal

Uses: Local anesthetic in toothache (inhibit nerve conducting), Anti-inflamatory , Bactericidal, Preparation of vanillin.

Ald. and Ketons Preparation: 1.By fractional dist. 2.By cooling if solid & in large amounts Assay 1- Condensation Reaction with hydroxylamine oxime Exss. Hydroxylamine HCL is added to known weight of oil, release HCL is titrated against standared. alc. KOH using methyl red for ald & dimethyl

Acyclic monoterpene ald. Citronellal Citral Source: Lemone oil Preparation: Fractional distillation. Citrus

Uses: Perfumes Not used in perfume Insect repellent but in Cosmetic preparation. Separation of citral a from citral b by sodium

Aromatic ald.

Benzald. Vanillin Source Oil of bitter almond Prep. Enzymatic hyd. vanilla pods Stem dist., pur. By calc. hyd. ,cryst. From alc /ferric sulphate , redistillation Uses Manuifacture of dye perfumes Perfumes Synthesis of vanillin

Vanilla pod Fermentation of Ext. with ether

flavoring,

Alicyclic bicyclic monoterpene

Fenchone Fennel Camphor lavender, rosmary

Preparation: By fractional dist. Steam dist, solidify on the wall (cooling) Uses: Counter irritant preservative Flavoring agents antiseptic Perfumes Synthesis of camphor 1- from pinene 2- borneol Reaction Camphor + sod. Metal in alc borneol & isoborneol

Ketons Acyclic (acetone) Alicyclic monoterpene Menthone Carvone Diosphenol (Buchu camphor) Mentha, mentha buchu caraway Buchu by NaHSO3 By oxime

 Alicyclic bicyclic monoterpene Fenchone Camphor Fennel lavender, rosmary By fractional dist. Steam dist, solidify on the wall(cooling) Counter irritant preservative Flavoring agents antiseptic Perfumes Syntesis of camphor 1- from pinenen 2- borneol Reaction

Test to differ. Bet. Natural & synthetic camphor + vanillin / HCL yellow /green /blue colour in natural Yellow only in synthetic Test for chloride negative with natural Positive with synthetic Separation of camphor & borneol + hydroxylamine oxime formation of camphor

Oxide & peroxide Monoterpene oxide Cineol ( eucalyptol) Source Eucalyptus Prep. Fractional distillation, then cooling Test + hydroquinone colorless prism or rhomboid crystal Uses Local anesthetic, Antiseptic, anti-inflammatory,expectorant

Monoterpenoid peroxide Ascaridole Sources oil of chenopodium Prep. Fractional dist under vacuum ( avoid high temp. to prevent explosion) Uses Anthelementic

Organosulpher compounds Allyl isothiocyanate Source black mustered Prep. Enzymatic hydrolysis. ,then distillation ( heaver than water) Uses Local rubefacient in plasters Flavoring agents