introduction
TRANSCRIPT
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%