Miscellaneous

Isoprenoids
By
Dr. Wael Afifi
 Bitters

Terpenoid Non-terpenoid
bitter bitter
 Mono
terpenoid
(10C)

Tetra Sesqui
terpenoids terpenoid
(40C) (15C)
Terpenoid
bitter

Tri Di
terpenoid terpenoid
(30C) (20C)
 Monoterpenoids
(Iridoids)

 Found in a wide variety of plants and in some animals.

*They are monoterpenes (С5Н8)2 biosynthesized from
isoprene.
*The iridoids are produced by plants primarily as a defense
against herbivores and infection by micro-organisms.

 Chemically, the iridoids usually consist of a сyclopentane

ring fused to a six-membered oxygen heterocycle (Pyran).
The chemical structure is exemplified by iridomyrmecin, a
defensive chemical produced by the Iridomyrmex genus,
for which iridoids are named. iridomyrmecin
 Physical and chemical properties of iridoids

Colorless crystals,
Bitter compounds,
They are soluble in water, ethanol, acetone, methanol
They occur as glycosides or complex epoxides in plants

Aglycons of iridoids are non-stable: they are sensitive to

enzymes and acids, while acetylated iridoids to alkali.
When treated by acids or under the influence of enzymes in
presence oxygen, iridoids form colored (dark blue or violet-
blue) non-solved in water products.
 Iridoids exhibit a wide range of bioactivities including:-
Bitter tonic e.g. Gentian
purgative,
antimicrobial, antiviral,
anti-inflammatory and analgesic e.g. Harpagophytum
immunomodulator,
sedative (valepotriates) e.g valeriana
Diuretic (catalpol и каталпозид),
antimutagenic,
antitumor (valtrate)
Cardiovascular,
hypoglycemic,
antispasmodic.
 Test for identification
 Trim and Hill’s test:
Iridoids + trim and hill’s reagent ( 1ml 0.2% aq. CuSO4 + 10 ml
acetic acid + 0.5 ml conc. HCl) Blue color

 Classification:
 Iridoid glycosides (e.g. aucubin, geniposide)
 Secoiridoid glycosides (e.g. gentiopicroside)
 Nonglycosidic iridoids (e.g. valeprotriates)
 Iridoids are formed in plants by an alternative cyclization of geranyl
diphosphate. The structures of these compounds are based on a
cyclopentan-[C]-pyran skeleton, carbocyclic iridoids, and oxidative
cleavage at the 7,8-bond of the cyclopentane moiety affords the so
called secoiridoids.
 On biogenetic grounds the iridoid formation may be considered to
start from iridodial cation and follow diversification through 27
different routes.
 Iridoids have been used as chemical markers for the Corniflorae,
Gentianiflorae, Loasiflorae and Lamiiflorae superorders.
6 4
5
3
7 A B
9
O2
8 1

Сyclopentanpyran

Iridodial
 Classification
1. Cyclopentan types
According to number of C atom in skeleton of aglycon they could be divided on 4
types: С8 , С9 , С10and С14.

O O O O

OH O -R O- R O -R

Iridodial С10-Iridoid С9 - Iridoid С8 - Iridoid

COOCH3 OH

HO
O O
Iridoids are typically found in plants as
glycosides, most often bound to glucose. CH3 O Glu CH2OH O Glu
Loganin Aucubin

2. Seco-iridoids. Cleavage of a bond in the cyclopentane ring gives rise to seco-

iridoids. O
COOCH3 O O
COOCH3
O
C
H O O O
O
HO
O Glu OH O- Glu
O Glu

Secologanin Gentiopicroside Oleuropeine

 Classification
3. Iridoids of plants from family Valerianaceae
Bicyclic monoterpenes or valepotriates (“Valeriana - Epoxy - triester”).

CH2 O C CH3 CH2 O C CH 3

O O
R2O R2O
O O

O R1 O O R1
O
Valtrate Dihydrovaltrate
R1=R2 – Isovalerianic acid R1 – Isovalerianic acid;
R2 – Acetoxyisovalerianic acid

COOCH3
Indole alkaloids

4. Iridoids-alkaloids – complex of indole alkaloids,

Secoiridoids
containing as non-amine part iridoid (determine in
plants from family Rubiaceae, Apocynaceae)
 I- Iridoids Glycosides
Aucubin
Source: from Aucuba japonica and plantago asiatica.
Properties:
 Colorless needles, soluble in water, methanol and ethanol
 On hydrolysis with β-glucosidase, it yields aucubigenin and Aucuba japonica
glucose.
Uses:
 Aucubin has a Hepatoprotective while aglycone has antitumor
activity and antibacterial activity against Staph. Aureus.

Plantago asiatica
 Genioposide Harpagide and Gentiopicroside
Harpagoside (Gentipicrin)
Occurrence Gardenia jasminoides Harpagophytum Gentiana lutea
procumbens
Chemical nature (1-Iridoid glycoside) (2-Secoiridoid glycoside)

Uses Anti-inflammatory and Anti-inflammatory, anti- Bitter Stomachic, Tonic,

analgesic rheumatic and analgesic antimicrobial and
antitumer
Chemical test + 10% HCl give
reddish violet color.
Structure
 Valeprotriates Valtrate and Didovaltrate

Occurrence Valeriana officinalis

Chemical (3-Non-glycoside Iridoid )

nature EPOXYIRIDOID ESTERS OR TRIESTERS IRIDOIDS
Uses Sedative and Both Sedative and valtrate is
tranquilizer tranquilizer

Structure
 Sesquiterpene Lactones

General Characters:
Biogenetically derived from farnesyl
pyrophosphate (FPP).
May be acyclic (linear), mono-, bi-,
tricyclic.
Colorless, bitter, toxic and relatively soluble
in water.
May be responsible for skin allergies.
May posses anticancer, antimicrobial and
antimalarial activities.
 Germacranolides Eudesmanolides Guainolides Pseudoguainolides

Cnicin Parthenolide Santonin (Keto-type) Artabsin Ambrosin and damsin

Holy thistle Feverfew Santonica flower Herba absinthii Damsissa (Ambrosia

‫ش‬C‫م كو‬C‫كراب‬ ‫ ةرهز‬C‫ألا‬C‫ق‬C‫ح‬C‫ناو‬ ‫شال‬C‫ال حي‬C‫ناسرخ‬C‫ى‬ maritima) ‫ابن‬C‫سمدال ت‬C‫ةسي‬

-Strong anti- -Anti- Anthelmintic for round Antispasmodic in renal colic

inflammatory inflammatory, worm
but is toxic. arthritis,
-Stimulate migraine
appetite
 Unusual-types of Sesquiterpene lactones
Artemisinin Gossypol
Artemisia annua Seeds of cotton (Gossypium species)
Endo-peroxide sesquiterpene Dimeric sesquiterpene

Antimalarial due to its Endo-peroxide Male contraceptive by alteration of

moiety. sperm maturation (L-form is only active)
 Diterpenoids
Derived from four isoprene units.
Found in plant, animal and insect world.
Have antihypertensive, antitumor, antibiotic and Anti-HIV
activities.
Classification:
Monocyclic Bicyclic Tricyclic Tetracyclic Macrocyclic Diterpene
lactones

Zoapatanol -Labdane-type -Pimarane-type. -Aconitine -Taxol -Ginkgolides

(forskolin) -Abietane-type -Stevioside -Tiglianes (Ginko biloba)
-Weight loss (natural -Neuroprotective
sweetner) -Anti-platelets
Triterpenoids (30C) Tetraterpenoids (40C)
-derived from squalene - Most important among natural terpenoid are yellow,
-abundant in nature particularly in resin orange red carotenoid pigments isolated from orange,
tomato, carrots, capsicum and brown algae.
1) Aliphatic e.g. squalene *Test for identification
2) Tetracyclic e.g. limonoids, cucurbitacins -CHCl3soln of carotenoids+85% H2SO4 blue col.
(Ant-tumor activity) -Carr-Price test:
3) Pentacyclic e.g. oleanolic acid, (CHCl 3soln + Antimony trichloride gives
glycyrrhetic acid. blue col.)
4) Quassinoids. -with conc HCl gives dark blue col.

Lycopene

Β-carotene