Professional Documents
Culture Documents
Nomenclature of plant
constituents
Systematic nomenclature is difficult due to
complexity of structure. Naming is based on
trivial nomenclature.
Root names are derived from:
1. Name of the discoverer
alkaloid after Pelletier
e.g.
Pelletierine
Classification of plant
constituents
Plant constituents occur as:
alkaloids ..
Classification of plant
constituents may be according
:to
A. Pharmacological
[analgesics,
laxatives,
etc..]
activity
cardiotonics
B. Biosynthetic
origin,
solubility
properties & key functional groups
C. Chemistry
properties
&
common
physical
1.
Volatile oil
Fixed oil
Volatilization at
ordinary
temperature
Volatile
Non-volatile
Solubility
Soluble in
organic solvents
(ether, CHCl3) &
alcohol
Limited
solubility in
organic
solvents, almost
insoluble in
alcohol
Stain on filter
paper
Transient
Permanent &
greasy
Composition
Complex
mixtures of
hydrocarbons &
oxygenated
compounds
Triglycerides of
fatty acids e.g.
palmitic, stearic,
..oleic
Response to
long exposure to
air & light
(oxidation)
Resinification
Rancidity
Historical
In ancient Egypt: embalming process
(antibacterial properties of essential oils &
resins).
In the Roman culture: aromatic essences in
massage & baths.
Incenses: [in temples, churches & mosques]
consist of resins rich in volatile oils
In folk medicine: inhalation of aromatics as
tranquilizers (e.g. incenses in case of
irritability) or stimulants (e.g. onions in case
of fainting)
:Botanical sources
Mainly in higher
plants
Especially in
Pinaceae, Lauraceae,
Rutaceae, Myrtaceae,
Labiateae,
Zingiberaceae,
Umbellifereae, &
Compositeae.
Combined with:
Sugars glycosides
Gums, resins or both oleo-gums,
oleoresins or oleo-gum-resins.
peppermint
Barks e.g. cinnamon
Woods e.g. sandalwood
Roots e.g. vetiver
Rhizomes e.g. ginger
Fruits e.g. umbelliferous & citrus
Seeds e.g. cardamon
Common Physical
Characters
1. Colorless, pleasant smelling liquids,
volatile at room temperature
2. Steam distillable
3. High refractive index
4. Mostly optically active
5. Density < water (i.e. lighter than
water) except for few ones
6. Immiscible with water, but sufficiently
soluble to impart a fragrance to water
aromatic waters [hydrosols]
7. Soluble in alcohol & common organic
solvents
8. Darken in color if exposed to air &
light (resinification)
Exceptions
1. Oils of cinnamon, clove & winter
green are heavier than water
2. Oils of anise & rose solidify just
below room temperature (15 &
18oC, respectively)
3. Oils containing azulenes are colored
(e.g. oil of chamomile is blue).
Chemical Composition
V. O. are complex mixtures of hydrocarbons
& oxygenated compounds [alcohols, phenols,
ethers,
aldehydes,
ketones,
oxides,
peroxides & esters]. All of these contribute to
the odor & physiological activity of the oil.
compounds,
Variation in Physico-Chemical
Characteristics
Most important influencing factors are:
2.
3.
4.
Distillation
Water Distillation
Sponge Method
Steam Distillation
Ecuelle a piquer
Method
Extraction
Enzymatic
Hydrolysis
Machine Processes
Pneumatic Method
Maceration Method
Distillation methods
Principle
vapor
Distillation methods
Application: preparation of thermostable
oils, present in large amounts & not rich in
esters (e.g. oils of turpentine, peppermint,
cardamon, anise, eucalyptus)
Types of distillation:
1.Water-distillation
2.Steam distillation
Water-and-steam distillation
Direct-steam distillation
Distillation: Terminology
Hydrodiffusion = process by which water or
steam penetrates the plant tissues to take over
the oil
Distillation methods
H2 O
Distillation
Steam Distillation
Direct Steam
Plant material
Fresh ( i.e.
containing moisture)
Commercial
preparations
Oils of clove,
cinnamon &
citronella
Oil of peppermint
Mode of
charging
Plant material
dipped in H2O
Steam
pressure
-H2O is absent.
-Steam is introduced by
pipes & forced through
the plant material
placed on perforated
trays
atmospheric
Can be modified
100C
Can be modified
Temperature
Rate & yield
Relatively low
Advantages
-Least expensive
Better
The best
Hydrolysis is
Distillation apparatus
Consists of 3 parts:
1. The distillation
chamber made of
stainless steel free
from any Fe+++ ions to
avoid degradation of
the oil constituents
darker oils.
2. The condensing system
3. The receiver e.g.
Florentine receivers
which allow separation
of the oily layer from
water in the distillate
(oils lighter or heavier
than water)
Purification
(Rectification) of
distilled oils
Florentine
Receivers
Bad
smelling or
dark
Remarks
1. Distillation should be done just after comminution [ i.e.
reduction in size, crushing, powdering) prevent loss by
evaporation or deterioration of the oil.
2. Coarse comminution increase "Hydrodiffusion" oils with
better yield & quality.
3. High temperature & water distilled oils differing in
composition from natural oils [artifacts].
4. Insufficient distillation time (shorter) fractionation of the
oil.
5. Hydrolytic products (e.g. lower alcohols & acids) are watersoluble & remain in the distillation chamber.
6. Steam volatile impurities e.g. amines & furfural (degradation
product of carbohydrates) contaminate the final product.
7. Sensitive constituents could be affected by boiling water e.g.
Esters hydrolyzed.
Tertiary alcohols dehydrated hydrocarbons.
Unsaturated hydrocarbons polymerized.
Applications
Preparation of heat sensitive oils, present
in large amounts in outer peels of fruits
e.g. Citrus fruits (Rutaceae) as orange,
lemon & bergamot.
D- Machine processes
Based on the same principles as the above
3 traditional methods A, B & C but carried
out by machines.
Volatile solvent-extraction
Preparation of "floral concretes"
1. Solvents used: petroleum ether & n-hexane
2. Extraction (percolation or maceration at room
temperature, continuous hot extraction in a Soxhlet
apparatus at constant temperature)
3. Solvent removal (distillation under reduced pressure)
Percolator
Soxhlet
apparatus
Volatile solvent-extraction
Floral concrete = Fragrant constituents +
Fats + Waxes + Albuminous matter + Fat
soluble pigments e.g. "floral concrete" of
jasmine is semi-solid & yellowish-orange in
color.
Floral absolute = consists mostly of the
oxygenated constituents of the oil.
More
expensive
&
purified
corresponding concrete.
Preparation:
repeated
absolute alcohol
than
extraction
the
with
volatile oils
Solvents:
Lipids of high degree of purity e.g.
Fats (lard : tallow in a mixture 2:1)
Fixed (olive oil)
Techniques:
closely
arranged
in
Procedure:
1.
2.
3.
4.
5.
6.
Enfleurage Process
Flower Petals
Add
fat
mixture
[Lard & tallow (2 : 1)]
2) Triple extract
[alc. solution of vol. oil +pigments +traces of fats]
Evaporation of alcohol
or fractional distillation
3)Absolute of Enfleurage
[Semi-solid, alcohol-free product]
Dilution with
H2O +NaCl
4)Volatile oil
Jasmine
flowers
Enfleurage Process
Cold Enfleurage
Hot Enfleurage
Process
Applications
Advantages
rich
Disadvantages
High
in method
temperature
(apparatus,
&
presence
of
thermostable
constituents
of heat)
the constituents.
Scarificatio
For preparation of
-Carried at room
Expensive due to
n&
temperature
need of high
Expression
amounts
in
peels
fruits
of
rich
in
outer
number of
&
heat-
more natural
sensitive
workers
odors.
constituents.
Extraction Suitable
for
fresh material
with
heat-sensitive oils
-Carried at room
Expensive due to
or low
temperature
present in small
amounts
or high number
of workers.
Gaultheria sp.
Non-volatile
Glycoside
Volatile
aglycone
Other hydrolytic
products
Hydrolytic
enzyme
Gaultherin
Methyl
salicylate
Primeverose
(Xylose + Glucose)
Gaultherase
Monotropin
Glucose
Methyl
salicylate
Betula lenta
(Betulaceae)
Gein
Eugenol
Glucose
-Glucosidase
Brassica nigra
(Brassicaceae)
Sinigrin
Allyl
isothiocyanate
Glucose +
Potassium acid
sulfate
Myrosin
Vanilla
planifolia
(Orchidaceae)
Glucovanillin
Vanillin
Glucose
-Glucosidase
Amygdalin
Benzaldelhyde
Gentiobiose
(2 glucose units) +
HCN
Amygdalase &
Emulsin
Geum
urbanum
(Rosaceae)
Amygdala
amara
(Prunus
amygdalus,
Rosaceae)
3.
2 HCN + Ca (OH) 2
Volatile
3 Ca (CN) 2 + FeSO4
Ca (CN)2 + 2H2O
Non-volatile
Determination of
percentage of volatile
oil in plant material
oils are
absolute
(dl).
Natural compounds are generally
Pycnometer
Polarimeter
Abbe
refractometer
2.
3.
4.
chain
Each
group
includes
non-oxygenated
(hydrocarbons) & oxygenated compounds.
Oxygenated
constituents
are
generally
responsible for the characteristic odor of the oil.
Removal of terpenoid
hydrocarbons
Removal
of
most
terpenoid
hydrocarbons
2.
3.
Terpeneless oils
Oils
from
terpene
which
most
More
expensive
natural oils
2.
Richer
in
compounds.
than
oxygenated
3.
More
soluble
in
strength alcohols.
4.
5.
low-
An isolate is a
single chemical
substance isolated
from the oil
Oleoptene &
Stearoptene
1. Stearoptene
solid
fraction
separating
on
cooling a v.o. (previously
known
as
camphors),
consists of 1 or more solid
(mainly
oxygenated
)
compounds
2. Oleoptene
=
remaining
liquid
fraction,
mainly
formed of hydrocarbons
Physical
methods
(cooling,
fractional
distillation, fractional crystallization &
preparative gas chromatography)
to
presence
of
Derivatization:
1.Alcohols esterification phenyl urethans or acid phthalates
2.Carbonyl compounds derivatives e.g. crystalline bisulfites,
semicarbazones, phenyl hydrazones & oximes.
Terpenoids (Terpenes)
They constitute the largest known group of
secondary metabolites.
3
C
h
t
C 2
CH3
Abbreviated structure
h=head, t=tail
Theoretical
Isoprene
Isoprene
Isoprene
Monocyclic
Acyclic
monoterpene monoterpene
Bicyclic
Monoterpene
Isoprene
2.
3.
4.
5.
6.
Azulenes (C15H18)
1.
2.
Nomenclature of terpenoids
are
2.
3.
4.
Acyclic
sesquiterpenoids
derivatives.
5.
6.
are
2,
6-dimethyl
carane,
octane
pinane,
trimethyldodecane
Myrcane
p-Menthane
m-Menthane
Trimethyldodecane
Thujane
Carane
Elemane
Pinane
Germacrane
Bisabolane
iso-Camphane
Humulane
Cadinane
Isomerism of Monoterpenoids
Structural isomerism due
to shift in the double
bonds, e.g.
Myrcene
Ocimene
Limonene
Terpinene
Limonene
Sylvestrene
Isomerism of Monoterpenoids
Geometrical
Geraniol
Optical
H
CH2OH
Nerol
Isomerism
can
be
OH
p-Cymene
OCH3
OH
Thymol
Carvacrol
O
OCH3
O
O H CO
3
OCH3
Anethole
Eugenol
Saffrole
OH
OCH3
Apiole
O
CHO
OCH3
CH2OH
OH
CHO
Vanillin Cinnamaldehyde Methyl salycilate