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OH
Me o
NMe
NO2
NMe
H
OH
(-)- Ephedrine
Sec. alk.
H
H
Ne2M
Me
Tubocurarine
Auaternary alk.
H2C
CH
CH2
O
NMe
C
H
H2C
CH
CH2
CH2OH
The nature of the N atom affects the properties, The derivatisation and the
method of isolation of the alk. From plants.
in the root
transported
Alk. Are oftenly occur in the form of salt e common a, e.g: acetic, citric, oxalic
or tannic.
Salts of special acids, examples:
1) Meconic a (Opium alk.)
2) Cinchotannic a (Cinchona)
3) Aconitic a (Aconite)
4) Gluco alk e.g:Solanine
General properties:
1) Most alk. are crystalline comp. odorless, colorless, non volatile.
they contain C, H, N, O few oxygenated alk.
Salts e
Alkali hydroxi
NH4
or nNa.CO3
Free base
5) Some alk. Neutral or slight acidic reaction can not form salts.
e.g: Ricinine, Theophylline.
6) Amphoteric alk. Contain-COOH gp. A narceine or-OH gp. as morphine.
W
7) Weak basic alk. e.g: caffeine, narcotine, papaverine, piperine from salts
Are unstable.
Solubility of alkaloids:
In fact, the differences in sdubility between alks. And their salts strongly facilitate the
process of isolation and separation of the alks. From plant and from non-alkaloidal
subst.
Optical Isomerism:
Alks are optically active comp.(many of them contain at least one
asymmet C-atom).
The pharmacological activities are usually more e laevorotatory isomers
than e the dextrorotatory e,g: D(-)- ephedrine 3 fold stronger than D(+)ephedrine (3:1) arterial B.p.
Some exceptions:
d-tubocurarine (dextrorotatory) is the medicinally active.
B) wagners reagent.
C) Hagars reagent
D) Gold chloricle
E) Dragendoeffs reagent.
2) Alkaloidal coloring reagents:
(The rough dehydration or oxidation of the alks)
A) Marquis reagent.
B) Mandalin R.
C) Froeheds r
D) Erdmanns R.
Marc
Aquous layer
(test to N-Oxides)
CHCL3
Aq.Layer (Alkaloid at )
Add NH4OH and extract with CHCL3
CHCL3
(Alkaloid bases; to be separatedchromatography)
Aq.Layer
Procedure III
General plant material
Extract with water or aqueous alcohol
containing acid
Marc
Aqueous
(alkaloid salts)
Shake with CHCL3
Aqueous layer
CHCL3 extract
(Alkaloid salts)
(pigments and impurities)
1- Alkalinize with NH4OH.
2- Extract with CHCL3
CHCL3
(Alkaloid bases;
separate by chromatography)
Aq.Layer
1) Volumetric methods.
a) (Acid base titration).
Add measured volume of stand acid, exces acid = stand alkali using
methy red.
B) (Non aqueous titration).
In non aqueous meduim using glacial acetic a , anhydrous CHCL3or
ether.
Advantages:
1) It is rapid (compared to the gravimetric methods).
2) Sensitive as it can determine alks. In trace amounts.
2) Gravimetric methods:
Plant material
Ext.
alks. dried
3) Chromatographic methods:
A) PC, TLC, CC.
B) Advanced GLC (for thermostable volatile alk. or volatile derivative of
non-volatile alks.)
C) HPLC ( for non volatile or thermolabile alks.
steam distillation.
5) Flourimetric methods:
For fluorescent alks. or alks that forms fluorescent derivative e certain
reagents.
Quinine and quinine dissolved in oxygenated acid.
Reserpine in hydrogen peroxide.
Repeated crystallization
Alkaloid free
Magers R (Hgcl2)
Dragendorffs
e alk.
e alk.
complex
complex Baco3
H2s
Alk.
free Alk.
Pseudo alkaloids:
Unrelated to amino acids. They are considered as alkaloids because of their
pharmacological importance and they contain nitrogen. E.g: purine alk. And
colchicuie .
Most of these alk. Derived from sterols, nicotinic or purines.
False alkaloids:
W
false + ve test e alkaloidal reagents but they are not alk.
e.g: proteins, some amino a, conjugated = bonds.
Classification of Alkaloids:
1) The botanical origin of alk.:
e.g: Solanaceous alk., Cinchona alks.,Ergot alks.
2) The pharmacological action of alks:
CNS stimutant alk, narcotic alk.
3) The amino acids from w alks. Are biosynthesized in the plants:
Ornithine derived alk., tryptophane derived alks., alanine derived alks.
4) The chemical structure of the alks.:
Non heterocyctic alk.
a typical alks or proto alk.
heterocyctic alks.
e.g: phyrrole
e.g: ephedrine
piperine
colchicine
pyridine
Nomenclature of alks.:
1) Name of the plant yielding them.
e.g:atropine (Atropa belladonna), cocaine (coca),
ergotamine (Ergot)
2) The name of scientist who discovered the alk. Pelletierine (after pelletier).
CH3
N
B
Meo
A
Meo
O
C
OMe
OMe
Tropolone st.
Non basic alk. (very weak base alk.).
Aromaic ring A e 3 methoxyl gp.
7-membered ring B e acetylated amino gp.
is
Tropolone ring C hose hydroxyl gp.
Methylated.
Isolation of Colchicine:
Powdered seeds oor cotms
90% alc.
alc. Ext.
Conc.
Alk. ex. e
CHCl3
Colchicine CHCL3
A 60-70 C for long time
yellow
dirty violet
brown
yellow
Dehydration of tissues
(a rhiazide diuretice)
Colchicine