Transcript 1. History, recent condition and market of essential oils

INTRODUCTION TO
GBPP
TEKNOLOGI MINYAK ATSIRI DAN
FITOKIMIA

Pengenalan minyak atsiri
Pemanfaatan, jenis, definisi, komponen atsiri

Penggolongan senyawa dalam
minyak atsiri
Terpenoid, benzen, rantai lurus,
senyawa N,S

Reaksi senyawa minyak atsiri
Esterifikasi, reduksi, oksidasi, hidrolisis,
adisi

Isolasi/Ekstraksi dengan metode penyulingan
Prinsip, tipe kondensor, peristiwa, jenis penyulingan,
keunggulan, kerusakan, faktor yang mempengaruhi, alat
dan proses penyulingan

Isolasi minyak atsiri dengan metode adsorbsi
Prinsip, faktor yang mempengaruhi daya adsorbsi,
rendemen dan mutu, pembuatan lemak, syarat bunga,
proses, cara adsorbsi enfleurasi dan maserasi

Isolasi minyak atsiri dengan metode solvent
extraction
prinsip, 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 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
World Major Essential Oils
approx. volume for 2007
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
Brian Lawrence- Perfumer & Flavourist v.34 January 2009
INDONESIAN AROMATIC PLANTS
Clove
Nutmeg
Benzoin
Cinnamon
Citronella
Clove
Nutmeg
Patchouli
Pepper
Cajeput
Clove
Nutmeg
Massoia
Cajeput
Cananga
Citronella
Clove
Cubeb
Galanga
Ginger
Kaffir
Lime
Patchouli
Clove
Sandalwood
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
Indonesian Essential Oil Production 2009
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)

No
Items
Output (MT)
Remarks
1
Clove/Stem Leaf
1,900-2,000
2
Patchouli
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
Mostly for derivatives
900-1,000
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
Distribution

In higher plants, different families as: Rutaceae,
Myrtaceae, Lamiaceae (Labiatae), Lauraceae
 Accumulate in all types of vegetable organs:
Flowers (rose), Leaves (eucalyptus),
Barks (cinnamon)
Woods (Sandalwood)
Stem bark (cinnamon)
Rhizomes (ginger),
Fruits (star anise),

Roots (vitiver.)
Seeds (nutmeg).
May occur associated with other constituents: gums
(oleogums), resins (oleoresins) gums & resins (oleogumresins)
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 aetherolea
Essential oils are derived from various sections of plants.
Berries
•Allspice
•Juniper
Seeds
•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-ylang
Peel
•Bergamot
•Grapefruit
•Lemon
•Lime
•Orange
•Tangerine
Root
•Valerian
• Vetiver
Decomposition
In 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 oils
i.
Steam distillation
ii.
Expression
4 Main types of volatile oils
i.
Concretes
ii.
Pomades
iii.
Resinoids
iv.
Absolutes
CONCRETES
Prepared 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.
RESINOIDS
Prepared 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 noncrystalline 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
Essential Oils
obtained by
Distillation
Oil
Aromatic extracts
obtained by
Expression
Solvent
Extraction
Enfleurage
Resinoids
Pomades
Citrus oil
Concretes
Absolutes
Enfleurage
absolutes
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 Sources
Indigenous to the Molucca
Islands (Spice Islands)
Cultivated in Indonesia,
Malaysia & the West
Indies.
NUTMEG OIL
Nutmeg oil is distilled from the
kernels of Myristica fragrans.
CONSTITUENTS
Pinene
Sabinene
Camphene
Dipentene
Safrole
Eugenol & eugenol derivatives
Myristicin – a benzene: toxic to
humans (large does of nutmeg
or nutmeg oil may cause
convulsions).
MACE – CONSTITUENTS
Consists 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 antibacterial 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, Tannins
Triterpene 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
O
HO
O
O
ETHYL ISOEUGENOL
O
O
O
O
O
O
O
METHYL
ISOEUGENOL
ISOEUGENYL
ACETATE
PROPENYL
GUAETHOL
O
H
O
HO
VANILLIN
BENZYL ISOEUGENOL
O
O
O
O
O
O
O
CARYOPHYLLENE
ACETATE
O
O
HO
HO
EUGENYL ACETATE METHYL EUGENOL ISO EUGENOL
BENZYL EUGENOL
DIHYDRO
EUGENOL
Distillation
CH3
H
H 3C
O
H
CH2
Fractionation
HO
Acetylation
EUGENOL
Isomerisation
Methylation
CH3
CARYOPHYLLENE
Hydrogenation
CLOVE OILS
Oxidation
Benzylation
CLOVE BUD/LEAF/STEM
Ethylation
Demethylation
CINNAMON: Cinnamomum zeylanicum
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
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
CHARACTERISTICS
Colourless or pale yellow
liquid
Aromatic & 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%)







Gingerol – pungent component –
Anti-inflammatory
Shogaols – increases bile
secretion
Sesquiterpene HC’s




Camphene
Cineole
Citral
Borneol
Zingiberene & Zingiberol
(Sesquiterpene alcohol)
Resins
Starch
Mucilage
LEMON OILS - Oleum limonis
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; 23 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
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 nonpharmaceutical purposes.
Oleum limonis - CONSTITUENTS
Terpenes – mainly
limonene
Sesquiterpenes
Aldehydes (Citral &
Citronella)
Esters
Lemon oil has a
tendency to
resinify and
should be
protected from the
action of air & light
as much as
possible.
TERPENELESS
LEMON OIL
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
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
3-METHYLBUTYL O-HYDROXYBENZOATE
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%
5%
5%