Distribution of alkaloids

• In the plants kingdom, the alkaloids appear to have a

restricted distribution in certain families and genera.
• Among the angiosperms, the Apocyanaceae,
Papaveraceae, Ranunculaceae, Rubiaceae, Solanaceae,
and beberidaceae are outstanding for alkaloids-yielding
plants.
• Although it has been claimed that monocotyledons do not
produce alkaloids, investigation indicate that the
Amarylidaceae and Liliaceae are two of the most
promising families in which to search for alkaloids-
yielding plants
• Specific alkaloids are ordinarily confined to specific plant
families (hyoscyamine in Solanaceae, colchicine in
Liliaceae).
• There are an exception to this rule such as:-
• 1. Nicotine, which is found in a number of widely scattered
plant families.
• 2. Ergot alkaloids in the fungus Claviceps pupurea
•  Alkaloids may occur in various parts of the plants
• 1)In seeds ( physostigma, areca).
• 2)In underground stems ( sanguinaria).
• 3)In roots ( belladonna root).
• 4)In rhizome and root ( ipecac, hydrastic).
• 5)In barks ( cinchona).
• 6)They also found in fungi ( ergot).
Classification of alkaloids
1. True alkaloids (characterized by a heterocyclic ring with
a nitrogen atom within this ring and are derived from amino
acid).
2. Proto alkaloids (characterized by absence of the
heterocyclic ring but derived from amino acid). As
Ephedrine: It has the N-atom only in the side chain and not
embedded in the aromatic ring
3. Pseudo alkaloids (characterized by a heterocyclic ring
with a nitrogen atom, but are not derived from amino acids)
(steroidal alkaloids).
• In general the alkaloids are classified according to the chemical structure into two
broad division:-
• A.Non-hetrocyclic or a typical alkaloids or biological amines.
• B.Hetrocyclic or typical alkaloids divided into 14 group according to their structure:-
• 1.Pyrrol and pyrrolidine.
• 2.Pyrrolizidine.
• 3.Pyridine and piperidine.
• 4.Tropane.
• 5.Quinoline.
• 6.isoquinoline.
• 7.Aprophine.
• 8.norlupinane.
• 9.indole.
• 10.indolizidine.
• 11. imidazole.
• 12. purine.
• 13. Steroid.
• 14. Terp
Nomenclature
• 1. From the generic name of the plant yielding them as atropine
( Atropa belladona).
• 2. From the specific name of the plant yielding them as
belladonine ( Atropa belladona).
• 3. From the common name of the drug yielding them as
ergotamine ( Ergot).
• 4. From their physiologic activity as emetine (Ipecac causes
emesis).
• 5. From the discoverer as pelletrine.
• A suffix is added sometimes to designate the alkaloids which
are similar in structure but differ in their stereochemistry. For
example quinine and quinidine.
• A prefix is added to designate alkaloids found in the same
plant example hydroquinine.
• Alkaloids name should end with ine.
Function of Alkaloids in Plants
• As strategically located poisonous agents in plants
thereby protecting them either against herbivorous
animals or insects,
• (b) As probable by-products of various detoxification
reactions representing a metabolic locking up of
compounds, otherwise harmful or detrimental to the plant,
• (c) As pronounced regulatory growth factors, and
• (d) As reserve substances in plant capable of supplying
nitrogen or other necessary elements to its economy.
General Characteristics of Alkaloids
• The general characteristics of alkaloids may be grouped
together in two categories, namely:
• (a) Physical characteristics, and
• (b) Chemical characteristics.
Physical Characteristics
• 1. the solubility of alkaloids both in water and organic
solvents:-
• it has been observed that the free alkaloid bases as such are
invariably found to be fairly soluble in organic solvents, such
as: either, chloroform, relatively non-polar solvents (hexane,
benzene, petroleum ether), immiscible solvent, lower alcohols
(methanol, ethanol); but they are either practically insoluble or
very sparingly soluble in water.
• Interestingly, the alkaloidal salts are almost freely soluble in
water, relatively less soluble in alcohol and mostly either
insoluble or sparingly soluble in organic solvents:
• Examples Atropine sulphate and morphine hydrochloride are
much more soluble in water than their corresponding bases
i.e., atropine and morphine.
, there are a few exceptions to the
above stated generalizations, namely
• (i) Certain alkaloid bases are water soluble, but these may be
solely regarded as exceptions such as: ephedrine, colchicine,
pilocarpine; the quaternary alkaloid-base like berberine and
tubocurarine; caffeine-base readily extracted from tea with
water.
• (ii) Narceine and pilocarpine are insoluble in organic
solvents, whereas morphine is sparingly soluble in organic
solvents, solubility in either 1:5000.
• (iii) Certain alkaloidal salts, for instance: lobeline
hydrochloride and apoatropine hydrochloride are found to be
soluble in organic solvent like chloroform.
• (iv) Some alkaloidal salts are sparingly soluble in water
whereas others are extremely water soluble, such as: Quinine
sulphate-soluble in 1:1000 parts of water, Quinine
hydrochloridesoluble in 1:1 part of water.
• 2. most alkaloids are colourless with exception berberine
(yellow), betaine (red)
• 3. most alkaloids are amorphous or crystalline and some
are liquids.
• The alkaloid usually possess bitter taste
Chemical Characteristics
• 1.Most of alkaloids are basic in nature due to the availability of
lone pair of electrons on nitrogen.
• 2. N-in the Molecule Besides, the other normal elements e.g.,
carbon, hydrogen, oxygen, the alkaloids must essentially
contain at least one N-atom. The number of N-atoms vary from
the bear minimum one in a molecule e.g., cocaine, to even five
in a molecule e.g., ergotamine. It has been observed that
these N-atoms are normally present as a part of the
heterocyclic ring in the alkaloid molecule or that contain the
N-atom in the aliphatic side chain.
• the N-atom may exist in the tertiary-amine form (R3N) e.g.,
morphine, reserpine; lesser in the secondary-amine form
(R2NH) e.g., ephedrine; and very rarely in the primary-amine
form (RNH2) e.g., nor-pseudo-ephedrine. Also in quartinary
amine R4N+
• The degree of basicity varies greatly, depending on the
structure of molecule and presence and location of other
functional groups.
• The basic character of alkaloids is enhanced if the
adjacent functional group are electron releasing while the
adjacent functional group are electron withdrawing like
amide they reduces the availability of lone electrons and
the electrons become neutral or acidic in nature.
• O-in the Molecule In addition to the common elements C,
H and N, a variety of alkaloids normally contains O-atom.
Invariably, these specific alkaloids are found in the solid
state, with a few exceptions where the oxygenated
alkaloids usually occur as non-volatile liquids, such as:
pilocarpine.
• Salient Features
• 1. The weaker bases, i.e., alkaloids having low pKa
values, shall require a more acidic medium to
• form their respective salts with the corresponding acid.
• 2. The strongly basic alkaloids i.e., those possessing high
pKa values, shall require comparatively
• low acidic medium to form their respective salts with the
acid.
Precipitation by Specific Reagents
• The alkaloid s like other amines form double salts with
compounds of mercury, gold, platinum and other heavy metals.
These double salts are usually obtained as precipitates. This
makes the basis for alkaloids reagents e.g.
• (i)Mayer’s Reagent (Potassium-Mercuric Iodide Test Solution):
• (ii) Wagner’s Reagent (Potassium Triiodide):
• (iii) Kraut’s Reagent (Modified Dragendorff’s Reagent or
Potassium Bismuth Iodide):
• (iv) Hager’s Reagent (a saturated of picric acid)
• The precipitates obtained are amorphous or crystalline of
avarious colors e.g. cream (Mayer), yellow (hager’s).caffeine
and some other alkaloids do not give precipitate
General Methods of Extraction and
Isolation of Alkaloids:-
• Using organic solvents for extraction e.g. ethanol, then
add acid to change the free alkaloids to salts, then add
base (ammonia) to turn it back to a free base the isolate it
by an immiscible organic solvent (chloroform, diethyl ether
(solvent ether) and isopropyl ether).
• If the plants is rich with alkaloids salts we turn it to free
base by maceration in ammonia.
• If the plant contains fats (especially seeds and roots), then
it should be defatted by maceration in petroleum ether).
• After isolation of the crude mixture of alkaloids it is purified
by several methods of purifications.
Purification of Alkaloidal Extract
• The main bulk of the crude alkaloidal extract is invariably subjected
to further purification by means of either anyone or combination of
the following methods:
• (a) Extraction with Acid Solution The extraction of the alkaloid
from the bulk of the crude alkaloid solution in immiscible organic
solvent is invariably carried out by shaking with an acid solution like
HCl and H2SO4.
• Subsequently, the acid solution is rendered alkaline with dilute
NH4OH solution to liberate the alkaloids which is then extracted with
an organic solvent. The solvent is removed under reduced
• pressure and the traces of moisture is removed with anhydrous
sodium sulphate.
• (b) Precipitation of Alkaloid with Precipitating Reagent:- The
usual precipitation of the alkaloid as a complex compound is
accomplished by the addition of a suitable precipitating reagent.
• The resulting alkaloidal complex is further purified by filtration,
recrystallization and ultimately decomposed to obtain the desired
free alkaloid(s).