INTRODUCTION TO

GBPP TEKNOLOGI MINYAK ATSIRI DAN

FITOKIMIA

Pengenalan minyak atsiri Pemanfaatan, jenis, definisi, komponen atsiri Penggolongan senyawa dalam

minyak atsiriTerpenoid, benzen, rantai lurus,

senyawa N,S Reaksi senyawa minyak atsiriEsterifikasi, reduksi, oksidasi, hidrolisis,

adisi

Isolasi/Ekstraksi dengan metode penyulinganPrinsip, tipe kondensor, peristiwa, jenis penyulingan, keunggulan, kerusakan, faktor yang mempengaruhi, alat dan proses penyulingan

Isolasi minyak atsiri dengan metode adsorbsiPrinsip, faktor yang mempengaruhi daya adsorbsi, rendemen dan mutu, pembuatan lemak, syarat bunga, proses, cara adsorbsi enfleurasi dan maserasi

Isolasi minyak atsiri dengan metode solvent extractionprinsip, deret eutropik pelarut, syarat pelarut, skema proses, daerah kritis penyebab loss pelarut

Isolasi minyak atsiri dengan metode press/kempa

Prinsip dasar, syarat bahan yang dikempa Analisis sifat fisikokimia

Bilangan iod, putaran optik, kelarutan dalam etanol, bilangan asam, bilangan ester, analisis komponen utama, analisis GC

Volatile Oils, Essential oils, Ethereal oils

Oily liquids, which are entirely or almost

entirely volatile without decomposition

Plant products, giving the odors and tastes

characteristic of the particular plant, thus

possessing the essence.

Ether like in their volatility.

ESSENTIAL/VOLATILE OILS

All official volatile oils are of vegetable origin.

Normally pre-exist in the plant – stored in a special secretory tissue (e.g. Citrus peel oil cells or oil ducts in umbelliferous fruits).

WORLD ESSENTIAL OIL TRADE World total essential oil value >USD 4 billion,

average growth/yr >5% Indonesian export >USD120 million Worls essential oil trade >300 items Indonesia >40 items, commercialized or

potentially

Essential Oil Production (MT) Major Source Derivative Prod.

Orange 51,000 Brasil, USA High

Cornmint 32,000 India, China High

Lemon 9,200 Argentine, Spain High

Eucalyptus 4,000 China, India Medium

Peppermint 3,300 USA, India Medium

Citronella 1,800 China, Indonesia Medium

Clove Leaf 1,800 Indonesia, Madagascar

High

Sassafras 1,800 China High

Lime 1,800 Mexico, Low

Lavandin 1,300 France, Spain Low

Patchouli 1,200 Indonesia, China Low

World Major Essential Oils approx. volume for 2007

Brian Lawrence- Perfumer & Flavourist v.34 January 2009

BenzoinCinnamonCitronellaCloveNutmegPatchouliPepper

CajeputCanang

aCitronell

aClove

CubebGalanga

GingerKaffir Lime

Patchouli

CloveNutmeg

CloveSandalwood

Massoia

Cajeput CloveNutme

g

INDONESIAN AROMATIC PLANTS

Indonesia is #1 grower of Cajeput, Cananga, Clove, Cubeb, Galanga,

Kaffir lime, Massoia, Nutmeg, Patchouli

Indonesia is # 2-5 grower of Benzoin, Cinnamon, Ginger, Pepper

Sandalwood, Vetiver

Total production 5000-6000 tons, USD 125-150 mill 80% of export comes from 3 main oils 60% essential oil, 30% derivative products for export, 10%

industry (food, cosmetic, consumer goods, pharmacy)

Indonesian Essential Oil Production 2009

No Items Output (MT) Remarks

1 Clove/Stem Leaf  1,900-2,000  Mostly for derivatives

2 Patchouli  900-1,000  

3 Nutmeg  350-400  

4 Citronella  300-400  Domestic > Export

5 Cajeput 200-300  Mostly for domestic

7 Gurjun  50-60  

6 Vetiver  25-30  

8 Cananga  12-15  

9 Massoia  12-13  

10 Eaglewood (aetoxylon sympetalum) 10-12

11 Lajagoa (alpina malaccensis) 3-4

12 Cubeb 2-3  

13 Sandalwood 1-2  

14 Kaffir Lime Leaf 1-2  

15 Agarwood 0.1-0.2  

FUNCTION OF VOLATILE OILS

In most cases, the biological function of the terpenoids of essential oils remains obscure – it is thought that they play an ecological role – protection from predators & attraction of pollinators.

Function

Attracting (help polination) or repelling insects

Protection from heat or cold As antibacterial agents Uses : Pharmacy, aromatherapy,

Perfumery, Food technology

LOCALIZATION

Synthesis & accumulation of essential oils are generally associated with the presence of specialized histological structures, often located on or near the surface of the plant:

- Oil cells of Zingiberaceae- Glandular trichomes of Lamiaceae- Secretory cavities of Myrtaceae or Rutaceae

- Secretory canals of Apiaceae or Astereraceae (Compositeae)

Localization

Usually in specialized histological structures

In higher plants, different families as: Rutaceae, Myrtaceae, Lamiaceae (Labiatae), Lauraceae

Accumulate in all types of vegetable organs:

Flowers (rose), Leaves (eucalyptus),

Barks (cinnamon)

Distribution

Woods (Sandalwood) Stem bark (cinnamon) Roots (vitiver.)

Rhizomes (ginger), Fruits (star anise), Seeds (nutmeg).

May occur associated with other constituents: gums (oleogums), resins (oleoresins) gums & resins (oleogumresins)

Berries•Allspice•JuniperSeeds•Almond•Anise•Celery•Cumin•Nutmeg oil

Bark•Cassia•Cinnamon•Sassafras

Wood•Camphor•Cedar•Rosewood•Sandalwood•Agarwood

Rhizome•Galangal•Ginger

Leaves•Basil•Bay leaf•Cinnamon•Common sage•Eucalyptus•Lemon grass•Melaleuca•Oregano•Patchouli•Peppermint•Pine•Rosemary•Spearmint•Tea tree•Thyme•Wintergreen

Resin•Frankincense•Myrrh

Flowers•Cannabis•Chamomile•Clary sage•Clove•Scented geranium•Hops•Hyssop•Jasmine•Lavender•Manuka•Marjoram•Orange•Rose•Ylang-ylangPeel•Bergamot•Grapefruit•Lemon•Lime•Orange•TangerineRoot•Valerian• Vetiver

An essential oil is a concentrated hydrophobic liquid containing volatile aroma compounds from plants. Essential oils are also known as volatile oils, ethereal oils or aetheroleaEssential oils are derived from various sections of plants.

DecompositionIn some cases the essential oils don’t pre-exist but

formed by decomposition of a glycoside-Benzaldehyde (amygdalin) in bitter almond-Allyl isothiocyanate(sinigrin) in black mustard

USES OF VOLATILE OILS

Therapeutically (Oil of Eucalyptus) Flavouring (Oil of Lemon) Perfumery (Oil of Rose) Starting materials to synthesize

other compounds (Oil of Turpentine) Anti-septic – due to high phenols

(Oil of Thyme). Also as a preservative (oils interfere with bacterial respiration)

Anti-spasmodic (Ginger, Lemon balm, Rosemary, Peppermint, Chamomile, Fennel, Caraway)

Aromatherapy

DEFINITION OF VOLATILE OILS

Volatile oils are products which are generally complex in composition, consisting of the volatile principles contained in plants, and are more or less modified during the preparation process.

Only 2 procedures may be used to prepare official oilsi. Steam distillationii. Expression

4 Main types of volatile oilsiii. Concretesiv. Pomadesv. Resinoidsvi. Absolutes

CONCRETESPrepared from raw materials of

vegetable origin (bark, flowers, leafs, roots etc.)

Extracted by HC type solvents, rather than distillation or expression – Becomes necessary when the essential oil is adversely affected by hot water or steam (e.g. jasmine).

Produces a more true-to-nature fragrance.

CONCRETES

Concretes contain about 50% wax and 50% essential oil (jasmine).

Ylang ylang (concrete volatile) contains 80% essential oil and 20% wax.

Advantages of concretes: they are more stable and concentrated than pure essential oils.

POMADES

True pomades are (volatile oil) products of a process known as enfleurage (hot or cold).

Enfleurage is used for obtaining aromatic materials from flowers containing volatile oils to produce perfume long after they were cut.

ENFLEURAGE: METHOD

A glass plate is covered with a thin coating of especially prepared and odourless fat (called a chassis).

The freshly cut flowers are individually laid on to the fat which in time becomes saturated with their essential oils. The flowers are renewed with fresh material.

Eventually the fragrance-saturated fat, known as pomade, may be treated with alcohol to extract the oil from the fat.

RESINOIDSPrepared from natural

resinous material (dried material) by extraction with a non-aqueous solvent, e.g. Petroleum ether or hexane.

E.g. Balsams – Peru balsam or benzoin; resins (amber or mastic); Oleoresin (copaiba balsam and turpentine); Oleogum resins (frankincense and myrrh)

RESINOIDS

Can be viscous liquids, semi-solid or solid.

Usually homogeneous mass of non-crystalline character.

Uses: in perfumery as fixatives to prolong the effect of a fragrance.

ABSOLUTES

Obtained from a concrete, pomade, or a resinoid by alcoholic extraction.

The extraction process may be repeated.

The ethanol solution is cooled & filtered to eliminate waxes.

The ethanol is then removed by distillation.

They are usually highly concentrated viscous liquids.

Aromatic material of natural origin

EnfleurageSolvent Extraction

Aromatic extracts obtained by

Pomades

Oil Citrus oil

Enfleurage absolutes

Resinoids

Absolutes

Concretes

Essential Oils obtained by

ExpressionDistillation

Physical properties

Possess characteristic odors Liquids and volatile at ambient temp. Soluble in common organic solvents. Sparingly

soluble in water, however sufficient to produce aromatic water.

Specific gravity (0.8-1.17), mostly lighter than water (clove and cinnamon are heavier).

Have high refractive index and most of them rotate the plane of polarized light.

Comparison between fixed oils and essential oils

Their volatility When smeared on paper Oxidation (resinified, fixed oil rancid) Chemical structure Saponification by KOH (NOT saponify)

CHEMICAL COMPOSITION

Volatile oils are divided into 2 main classes based on their biosynthetic origin

i. Terpene derivatives (formed via the acetate mevalonic acid pathway)

ii. Aromatic compounds (formed via the shikimic acid-phenylpropanoid route)

iii. Miscellaneous Origin

VOLATILE OIL COMPOSITION Mixtures of HC’s and oxygenated

compounds derived from these HC’s. Oil of turpentine – mainly HC’s Oil of Clove – mainly oxygenated compounds

EXCEPTION: Oils derived from glycosides (e.g. bitter almond oil & mustard oil).

Oxygenated compounds – responsible for the odour/smell of the oil. They are slightly water soluble – Rose water & Orange Water; more alcohol soluble.

Most volatile oils are terpenoid. Some are aromatic (benzene) derivatives mixed with terpenes.

Some compounds are aromatic, but terpenoid in origin (e.g. Thymol – Thyme)

NUTMEG & NUTMEG OIL

Definition: Nutmeg is the dried kernel of the seed of Myristica fragrans (Myristicaceae).

Geographical SourcesIndigenous to the Molucca

Islands (Spice Islands)Cultivated in Indonesia,

Malaysia & the West Indies.

NUTMEG OILNutmeg oil is distilled from the

kernels of Myristica fragrans.

CONSTITUENTSPineneSabineneCampheneDipenteneSafroleEugenol & eugenol derivativesMyristicin – a benzene: toxic to

humans (large does of nutmeg or nutmeg oil may cause convulsions).

MACE – CONSTITUENTSConsists of the dried arillus

or arillode of M. fragrans.

Description: bright red colour & lacks in aroma

CONSTITUENTS

Volatile oils (similar to that of nutmeg) – eugenol derivatives are the main active constituents – responsible for the anti-bacterial effects.

Also has 2 anti-microbial resorcinols (Malabaricone B and C)

Used for carminatives, flavouring, infantile diarrhoea (Tea of nutmeg – Ayurveda).

CLOVE

DEFINITION: Cloves are the dried flower buds of Syzygium aromaticum (Eugenia caryophyllus), (Myrtaceaea).

Cloves are 10-17.5 mm long.

The head consists of 4 slightly projecting calyx teeth, 4 membranous petals and numerous incurved stamens around a large style.

Odour: Spicy & Pungent

Taste: Aromatic

Oil of cloves is yellow or colourless, is slightly heavier than water.

CLOVE OIL - CONSTITUENTS

14-21% Volatile oils

mainly eugenol, isoeugenol, & acetyleugenol

Sesquiterpenes(α and β caryophyllenes)

Stigmasterol, Campesterol, TanninsTriterpene acids & esters, Glycosides

Oil of clove – like other volatile/essential oils – should be stored in a well-fitted, air-tight container, & should be protected from light & heat.

Derivatives of Clove Oil

EUGENOL

O

HO

ISO EUGENOLEUGENYL ACETATE METHYL EUGENOL

METHYL ISOEUGENOL

ISOEUGENYL ACETATE

CH3

CH3

CH2

H3CHH

CARYOPHYLLENE

O

OO

OO

O

O

O HO

O

O

O

O

O

O

O

BENZYL ISOEUGENOL

BENZYL EUGENOL

O

HO

OH

O

HO

CLOVE BUD/LEAF/STEM

CLOVE OILS

DIHYDRO EUGENOL

VANILLIN

CARYOPHYLLENE ACETATE

Distillation

Fractionation

Acetylation

Isomerisation

Methylation

Hydrogenation

Oxidation

Benzylation

Ethylation

Demethylation

ETHYL ISOEUGENOL PROPENYLGUAETHOL

O

O

O

HO

Individually scraped barks are placed inside each other

Consists of a single or double compound quill about 6-10 mm diameter

Thickness : good quality: Not > 0.5mm, bark: 10-40mm.

External surface: is yellow-brown, shining, wavy lines (pericycle fibres) and occasional scars & holes (leave/twig positions).

Inner surface: darker, longitudinally striated.

Odour: fragrant Taste: Warm, sweet & aromatic

CINNAMON: Cinnamomum zeylanicum

Cinnamomum - CONSTITUENTS

• Volatile oils (at least 1.2 %)

• Phlobaphenes• Mucilage• Calcium Oxalate• Starch

EUCALYPTUS

DEFINTION: Eucalyptus leaf consists of the whole or cut dried leaves of the older branches of Eucalyptus globulus, (Myrtaceae).

GEOGRAPHICAL SOURCES

Portugal, SA, Spain, China, Brazil, Australia, India & Paraguay.

CHARACTERISTICS & CONSTITUENTS

CHARACTERISTICSColourless or pale yellow

liquidAromatic & camphoraceous

in odour.Pungent & camphoraceous

in taste, which is followed by a sensation of cold.

CONSTITUENTS At least 70 volatile oils

(mainly cineole).

GINGER

Scraped/peeled herb has little resemblance to the fresh herb (loss in weight & shrinkage)

Cork cells – high starch content

Outer zone of flattened parenchyma & inner zone of normal parenchyma.

Oil cells scattered in the cortex.

Zingiber officinale - CONSTITUENTS Volatile oils (1 – 2%)

Camphene Cineole Citral Borneol

Gingerol – pungent component – Anti-inflammatory

Shogaols – increases bile secretion

Sesquiterpene HC’s Zingiberene & Zingiberol

(Sesquiterpene alcohol)

Resins Starch Mucilage

Definition: Dried lemon (Limonis Cortex) peel is obtained from the fruit of Citrus limon (Rutaceae).

Dried lemon peel occurs in spiral bands (2 cm wide; 2-3 mm thick).

The outer surface is rough & yellow; the inner surface is pulpy & white (anatomically similar to that of an orange peel).

Odour: Strong & characteristic

Taste: aromatic & bitter

LEMON OILS - Oleum limonis

LEMON OILS - Oleum limonis

Definition: Lemon oil is the oil expressed from the outer part of the fresh pericarp of the ripe or nearly ripe fruit of Citrus limon (Rutaceae).

Oil should be obtained by suitable mechanical means, without the use of heat, from the fresh peel.

Much oil is derived via steam distillation, but this process yields oil of inferior quality.

Distilled oil of lemon is much cheaper than that prepared by expression. Large amounts are used for non-pharmaceutical purposes.

Oleum limonis - CONSTITUENTS

Terpenes – mainly limonene

Sesquiterpenes

Aldehydes (Citral & Citronella)

Esters

Lemon oil has a

Definition: Oil prepared by concentrating lemon oil in vacuum until most of the terpenes have been removed, or by solvent partition. The concentrate is a terpeneless oil, which has a citral content of 40-50 %.

It is equal in flavouring to 10-15 times its volume of lemon oil

TERPENELESS LEMON OIL

tendency to resinify and should be protected from the action of air & light as much as possible.

TYPICAL FORMULA OF FRAGRANCE COMPOUND (JASMINE)

BENZYL ACETATE 50% 1-P-METHEN-8-OL 10% METHYL-2-AMINOBENZOATE

5% 4-(2,5,6,6-TETRAMETHYL-2-CYCLOHEXEN-1-YL)-3-BUTEN-2-ONE 5% 3-METHYLBUTYL O-HYDROXYBENZOATE 5% ALPHA-CINNAMALDEHYDE 5% CANANGA OIL 5% PETITGRAIN OIL 5% STYRAX

5% MUSK XILENE 3% RECTIFIED CLOVE LEAF OIL

2%ESSENTIAL OIL in FRAGRANCE COMPOUND: 10 – 25%

FRAGRANCE COMPOUND IN SOAP: 1 – 1.2%,

IN EAU de TOILETTE: 6-8%