ALKALOIDS

Alkaloid
:
Alkaloid: Difficult to
define
No definitive difference
between an alkaloid
and naturally occurring
complex amines.
Alkaloids: plant derived,
are alkali and contain at
least one N2-atom.
They also normally have
a significant
physiological action on
humans and animals
.

:



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.
- ( .) -

:Alkaloid Description
Contains nitrogen - usually derived
from an amino acid.

Bitter tasting, generally white solids

(exception - nicotine is a brown liquid).

They give a precipitate with heavy

metal iodides. Except Caffeine.

() (
)

Alkaloids are basic - they form water

soluble salts.
In plants, they may exist
in the free state, as salts or as Noxides.
Occur in a limited number of plants.
.

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Tests for Alkaloids

Most alkaloids are precipitated from

neutral or slightly acidic solution by
Mayer's reagent (potassiomercuric iodide
solution) Cream coloured precipitate.
Dragendorff's reagent (solution of
potassium bismuth iodide) orange
coloured precipitate.
Wagners reagent (iodine in potassium
iodide) red-brown precipitate
Hagers reagent (picric acid) yellow
precipitate
Caffeine does precipitate

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Occurrence Distribution &

of Alkaloids
:
Occur in bacteria and rarely in
fungi.
Some alkaloids occur in several
genera from different species,
but most occur in closely
related species.
Some occur in certain families ,.
All alkaloids of one plant will have
a common biogenenetic origin

-1
-2
)--, ( ,

. -3
-4

Chemistry of Alkaloids
The N2 atom can either be
1, 2, 3 or 4
(quaternary).

This N2 feature affects the

alkaloid derivatives which can
be prepared and the isolation
procedures

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:
Physical & chemical properties
The basicity of alkaloids depends on the
availability of the lone pair of e- on the
N2 atoms:
Because some alkaloids have a carbonyl
group on the amide, they can also be
neutral (colchicine & piperine).

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Basic characteristic renders complex

alkaloids unstable, so that in solution
they are sensitive to heat, light &
oxygen.
Basic character of alkaloids also allows
them to form salts with mineral acids
(such as hydrochlorides, nitrates and
sulphates) or inorganic acids (tartrates,
sulfamates).
Solid salts can be conserved well and are a
common commercial form of alkaloids.

,(

.....
MW: 100 900 , they are whit
crystals. In rare cases they are
coloured.

900 -100 -

Most bases which do not contain

O2 are liquid at room
temperature

- (
.)

All active except Purins

Soluble in concentrated
hydroalcoholic solutions
They give a precipitate with heavy
metal iodides. Caffeine, a purine
derivative, does not precipitate like
most alkaloids.

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.

Naming of Alkaloids
Numerous methods can be used to
name alkaloids
Generic plant name atropine
from Atropa belladonna
Specific name of the plant
cocaine from Erythroxylum coca.
Common name of the herb
ergotamine from ergot (rye)
Physiological action of the plant
emetine producing emesis
Other e.g. morphine derived
from ancient Greek mythology
Morpheus god of dreams

Extraction of Alkaloids
Extraction is based on the basicity of
alkaloids ( they normally occur in plants
as salts).
Herbs often contain other materials
which interfere with extraction
by forming emulsions.( waxes,
terpenes, pigments and other
lipophilic substances) avoided
by defatting
Extraction method normally depends on
the raw material, the purpose of
extraction & the scale on which is to
be performed.

For research purposes: chromatography

allows for quick and reliable results.

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-).... ,(
-

-
-

(
)
TLC plate

Extraction of Alkaloids
Organic solvent containing alkaloids (bases) is
separated from residue by alcohol
concentrated .
Solvent is stirred with an acidic aqueous
solution: alkaloids go into the solution as
salts. Impurities remain in the organic phase.
Repeated until the organic phase no longer
contains alkaloids.

Alkalinized with a base using an organic

solvent not miscible with water (chloroform).
Alkaloids precipitate and dissolve in the
organic phase. Extraction of aqueous phase
continues till all alkaloids have moved into
the organic phase (tested when Mayers
reaction on the aqueous phase becomes
negative).
This purification step may be carried out in a
separation funnel or in centrifugal extractors.

Organic solvent containing alkaloid bases

(drying over anhydrous sodium sulphate)
evaporated under reduced pressure. A dry
residue remains: total basic alkaloids

: -1

HCl H2SO4 +


+

Isolation of Alkaloids
Volatile liquid alkaloids (nicotine) are
isolated by distillation alkaloid is
distilled off in steam. Nicotine is an
important insecticide, and large
amounts are prepared from the
parts of the tobacco plant which is
not used for tobacco manufacture

: -2
) (

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: Isolation of Alkaloids
All methods of alkaloid extraction
yield impure compounds, so
alkaloids therefore have to be
separated.
TLC and HPLC are most
commonly used.

Chromatography is used for

complex alkaloids and if
only small amounts of
alkaloids are needed.

TLC silica (
)PC() gel
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* (
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Crystals of Hydrastine