Alkaloids

Phytochemistry II
PG 605
2021/2022
 Alkaloids

• Basic, organic, nitrogenous

compounds of plant origin
possessing a physiological
activity.
 Hegnauer’s classification
True alkaloids Protoalkaloids Pseudoalkaloids
Derived from amino acid Not derived from amino acid

(N) is not in
(N) in heterocyclic ring (N) in heterocyclic ring
heterocyclic ring
e.g. Strychnine e.g. Ephedrine e.g. Caffeine

OH O
CH3
H3C
N
N

NHCH3 O N N

CH3
 Detection of alkaloids
o Chromatographic techniques
Spots in TLC corresponding to alkaloids:
- Spraying with Dragendorff’s reagent
- Expose to I2 vapor (not specific)

o Chemical tests
i. Alkaloid precipitants + alkaloid soln amorphous or
crystaline ppt
ii. Alkaloid color reagent + alkaloid residue or pd Characteristic
color
I. Alkaloid precipitants (Heavy metals)
Mayer’s reagent Potassium- mercuric iodide Creamy white ppt
soln
Wagner’s reagent Soln of iodine in KI Reddish brown ppt
Hager’s reagent Sat soln of picric acid in H2O Yellow ppt
Dragendorff’s reagent Soln of potassium bismuth Orange to reddish
iodide brown ppt
Marme’s reagent Soln of potassium cadmium Yellow ppt
iodide

II. Alkaloid color reagents (H2SO4)

Froehd’s reagent Ammonium Molybdate/H2SO4
Mandalin’s reagent Ammonium Vanadate/H2SO4
Marqui’s reagent HCHO / H2SO4
Erdmann’s reagent HNO3 / H2SO4
Modified Dragendorff’s reagent Potassium bismuth iodide
Qualitative tests for identification of
selected alkaloids

oPapaverin o Eserine

oBrucine o Pilocarine
o Atropine
oQuinine
o Strychnine
oCaffeine

oEphedrine
 Papaverine
(Isoquinoline alkaloid)

1-Mayer’s test
0.5ml of alk Creamy white
+ precipitate
4 dps mayer's reagent
2- Conc HNO3 test
1-Evaporate on BWB
1ml alkaloid till complete dryness
solution
2- Cooling
3- 3 dps Conc HNO3
4- See color I 5- Evaporate on
BWB till complete
dryness
6-See color II of
the residue
3-Special test for papaverine
(Warren’s test)
1-Evaporate till dryness

1ml alkaloid 2-Cool

solution 3- One crystal of KMnO4
4-Crush with end of test
tube
5-2 dps of Marqui’s
reagent
One crystal

Bluish green

KMnO4
 H 3C
N

Atropine H CH2OH
Tropane alkaloid
O
O

1-Mayer’s test
0.5 ml alk soln Creamy white
+ 4 dp mayer’s reagent precipitate
 2- Conc HNO3 test (Vitali’s test)
1ml alkaloid 1-Evaporate on BWB till
solution complete dryness
colorless
2- Cooling
3- 3dps Conc. HNO3
4- See color I
5- Evaporate on
BWB till complete
dryness
Violet color which 6-See color II of the
fades by time residue

7- CooL
colorless
8- 3 dps alc KOH
Violet color fades by time
 Pilocarpine
(Imidazole alkaloid)

1-Mayer’s test
1 ml of alk
Creamy white
+
precipitate
4 drops of Mayer's
reagent
2- Conc HNO3 test
1ml alkaloid 1-Evaporate on BWB till
solution complete dryness
colorless
2- Cooling
3- 3dps Conc. HNO3
4- See color I
5- Evaporate on
BWB till complete
dryness
6-See color II of the
residue

7- CooL
colorless
8- 3 dps alc KOH
No Violet
2. Special test for Pilocarpine (Helch’s test)

Yellow color in
1 ml alkaloid solution Shake aqueous layer
2 dps H2O2
Violet color in
2 dps 1/300 K2Cr2O7 𝐂𝐇𝟐 𝐂𝐥𝟐 layer
1 ml 𝐂𝐇𝟐 𝐂𝐥𝟐
 O
Caffeine H3C
N
CH3

2,6 dioxy purine N

(Xanthine) alkaloid
O N N

CH3

1-Mayer’s test

0.5 ml alk soln No creamy white ppt

+ 4 dp mayer’s reagent
2- Special test for caffeine
(Murexide test)

Evaporate on BWB to Residue

1ml dryness
alkaloid cool
soln +2dp conc HCL
+ 2dp H2O2
Evaporate

Invert on
Yellow
Violet NH3 vapors Crimson
color
color red color
 Murexide test for caffeine

Violet
color
Crimson
red
color

NH3 vapors