INTRODUCTION TO SECONDARY

METABOLITES
Presented by Krishna Maniyalil
 INTRODUCTION
 Plants produce a vast number of different chemical compounds which are
broadly categorized by primary metabolites and secondary metabolites.
 Primary metabolites are essentials for the plants for their survival likely
sugar, proteins, amino acid etc. Thereafter secondary metabolites are the
products that are considered as waste substances of plants.
 Alkaloids are a large and complex group of highly diverse
natural products.
 name "alkaloids" basic nitrogen atoms in a heterocyclic

ring. They have low molecular weight.

(E.g. Datura),
Bark (E.g. Cinchona)
Seeds (E.g. Nux vomica)
Roots (E.g. Aconite)
Leaves (E.g. Tobacco)
Fruits (E.g. Black pepper)
 Alkaloids are crystalline in nature but few are amorphous solid (Example:
Emetine). Solid nature due to presence of O-atom in the ring structure.
 They mostly contain basic lone pair electron on nitrogen, hence they are
basic in nature (Some compounds like theobromine, theophylline are
amphoteric in nature)
 They contain one or more nitrogen in their structure and forms primary
amines (R-NH2; Example: Norephedrine), Secondary amines (R2-NH;
Example: Ephedrine), Tertiary amines (R3-N; Example: Atropine) and
Quaternary ammonium salt (R4-N; Example: d-Tubocurarine)
 Monocyclic alkaloids: They contain a single, unfused ring. Example: Nicotine

Bicyclic alkaloids: They consist of molecules with a 1,4 nitrogen bridged

cycloheptane structure. Examples: Atropine, Cocaine.

Polycyclic alkaloids: They are having more than two rings. Examples: Strychnine,
Cannabinol, Morphine, Codeine etc.
Heterocyclic Alkaloids:
Types of alkaloids, structures, examples, biological sources, family and uses of some
heterocyclic alkaloids
Non-heterocyclic alkaloids:
Based on Nature/Basicity: They are classified as:
 • Primary amines (R-NH2; Example: Norephedrine),
 • Secondary amines (R2-NH; Example: Ephedrine),
 • Tertiary amines (R3-N; Example: Atropine)
 • Quaternary ammonium salt (R4-N; Example: d-Tubocurarine)

 Basicity of alkaloids is as follows: R2-NH > R-NH2 > R3-N. The basicity of
alkaloids due to
presence of lone pair of electron on nitrogen. The basicity increases if the adjacent
group is electron releasing like alkali whereas the basicity decreases if the adjacent
group is electron withdrawing like carbonyl and amide group.
 Based on Hegnauer’s Classification:
 True Alkaloids: They are the alkaloids that derived directly from amino acid. They contain nitrogen in
their heterocyclic ring. They are basic in nature due to presence of lone pair of electron on nitrogen atom
and strong toxic in nature Quinine, Morphine, Atropine etc

Proto alkaloids: They do not have nitrogen in their heterocyclic ring. They are
derived from L-Tryptophan, Phenylalanine and Tyrosine
Examples: Ephedrine

Pseudo alkaloids
They are not derived from amino acids but derived from the precursors of amino acid (Non-amino acid
precursor). They have nitrogen in a heterocyclic ring (acquire nitrogen through transamination process.
Examples: Caffeine
 (D) Based on Taxonomical Origin:
Alkaloids are classified on the basis of the biological source. Examples: Quinine from bark
of Cinchona calisaya, Rauwolfia from roots of Rauwolfia serpentina, Morphine from dried
latex of Papaver somniferum etc.

Precipitation reactions
Vitali Morin Test
1. Stas-Otto method:
 Glycoside is an organic compound contains C, H, and O in
their structure. They are natural carbohydrate substances.
They are obtained from maximum higher plants but in less
quantity.
 Sugar part is known as glycone part whereas non-
sugar part is known as
 aglycone part or genin part. Due to presence of
aglycone part, glycosides give therapeutic
 activities. Sugar and non-sugar parts are linked with
glycosidic bridge, known as glycosidic
 linkage.
 (a) C-glycoside:
 Glycone-OH + HC –aglycone → Glycone-C-aglycone + H2O
 (b) O-glycoside:
 Glycone-OH + HO-aglycone → Glycone-O-aglycone + H2O
 They are common in higher in plants. Example: Senna,
 S-glycoside:
 Glycone-OH + HS–aglycone → Glycone-S-aglycone + H2O
They occurrence of this glycoside is in isothiacyanate glycoside like sinigirin in black
mustard formed by the condensation of sulphohydryl group aglycone to OH group of
glycone
 (d) N-glycoside:
 Glycone-OH + HN–aglycone → Glycone-N-aglycone + H2O
 They are mostly present in the nucleoside where the amino group reacts with OH group
 of ribose or deoxyribose resulting into N-glycoside
 (e) C and O-Glycosides:
This is one more type of glycosidic linkage where glucose molecule attached with
aglycone part by both C and O linkages. Example: Cascarosides from Cascara
 Stas-otto method:
 FLAVONOIDS
 They are 2-phenylbenzopyrones derivatives and produce a large number of physiological activities.
They may be described as a series of C6-C3-C6 compound
 Chemical Properties:
 • Chemically flavonoids are based upon a fifteen-carbon skeleton (C15) consisting of
 two benzene rings (A and B) linked via a heterocyclic pyrane ring (C).
 • They occur as aglycones, glycosides, and methylated derivatives.
 • Six-member ring condensed with the benzene ring is either a α-pyrone (flavonols
 and flavanones) or its dihydroderivative (flavonols and flavanones).
 • The position of the benzenoid substituent divides the flavonoid class into flavonoids
 (2-position) and isoflavonoids (3-position).
 • Flavonols differ from flavanones by hydroxyl group at the 3-position and a C2–C3
 double bond.
 • Flavonoids are often hydroxylated at positions 3, 5, 7, 2, 3′, 4′, and 5′. Methyl ethers
 and acetyl esters of the alcohol group are known to occur in nature.
 • The glycosidic linkage is normally located in flavonoid at position 3 and 7
 As per the Place of B-ring location:
 As per the location of the B-ring, they are three types like true flavonoids, isoflavonoid
 and neoflavonoid. True Flavonoids are derived from 2-phenylchromen-4-one (2-phenyl-l,
 4-benzopyrone) structure. Isoflavonoids are derived from 3-phenylchromen- 4-one
 (3-phenyl-1,4-benzopyrone) structure and Neo-flavonoids are derived from 4-phenyl_x0002_coumarine
(4-phenyl-1,2-benzopyrone) structure. True Flavonoids are also known as
 bioflavonoid due to origin from plants. Bioflavonoids are anthoxanthin i.e. mixture of
 flavones and flavonol
 They are naturally occurring non-nitrogenous compound.

have number of hydroxyls and carboxyl groups to form strong complexes with various
macromolecules.
They are mainly located in the vacuoles or surface wax of
plants
Recently, a third class of tannins has been identified, the phloro tannins, present in
many
species of dark brown algae such as kelps and rockweeds or sargassacean. It is also
available
in some red algae. These compounds are oligomers of phloroglucinol
(polyphloroglucinols)
and based on arrangement of the phloroglucinol monomers they are further classified.